次の XSD があるとします。
<?xml version="1.0" encoding="utf-8" ?>
<!-- XML Schema generated by QTAssistant/XSD Module (http://www.paschidev.com) -->
<xsd:schema targetNamespace="http://tempuri.org/XMLSchema.xsd" xmlns="http://tempuri.org/XMLSchema.xsd" elementFormDefault="qualified" xmlns:xsd="http://www.w3.org/2001/XMLSchema">
    <xsd:element name="elementB">
        <xsd:complexType>
            <xsd:sequence>
                <xsd:element name="FirstName" type="xsd:string"/>
                <xsd:element name="LastName" type="xsd:string"/>
            </xsd:sequence>
        </xsd:complexType>
    </xsd:element>  
</xsd:schema>
少なくともそれを行うには2つの方法があります。1 つ目は、継承と、シリアライザー アノテーションの操作方法に依存しています。
xsd.exe はこれを生成します:
//------------------------------------------------------------------------------
// <auto-generated>
//     This code was generated by a tool.
//     Runtime Version:4.0.30319.18034
//
//     Changes to this file may cause incorrect behavior and will be lost if
//     the code is regenerated.
// </auto-generated>
//------------------------------------------------------------------------------
using System.Xml.Serialization;
// 
// This source code was auto-generated by xsd, Version=4.0.30319.1.
// 
/// <remarks/>
[System.CodeDom.Compiler.GeneratedCodeAttribute("xsd", "4.0.30319.1")]
[System.SerializableAttribute()]
[System.Diagnostics.DebuggerStepThroughAttribute()]
[System.ComponentModel.DesignerCategoryAttribute("code")]
[System.Xml.Serialization.XmlTypeAttribute(AnonymousType=true, Namespace="http://tempuri.org/XMLSchema.xsd")]
[System.Xml.Serialization.XmlRootAttribute(Namespace="http://tempuri.org/XMLSchema.xsd", IsNullable=false)]
public partial class elementB {
    private string firstNameField;
    private string lastNameField;
    /// <remarks/>
    public string FirstName {
        get {
            return this.firstNameField;
        }
        set {
            this.firstNameField = value;
        }
    }
    /// <remarks/>
    public string LastName {
        get {
            return this.lastNameField;
        }
        set {
            this.lastNameField = value;
        }
    }
}
「注入」するxsi:schemaLocationには、新しいクラスを追加しelementA : elementBます。知らせ:
- System.Xml.Serialization.XmlRootAttribute のセットアップ
 
schemaLocationプロパティのセットアップ。 
テストプログラム:
using System;
using System.Collections.Generic;
using System.Linq;
using System.Text;
using System.Xml.Serialization;
using System.IO;
using System.Xml;
namespace ConsoleApplication2
{
    class Program
    {
        static void Main(string[] args)
        {
            elementB b = new elementB();
            b.FirstName = "P";
            b.LastName = "G";
            XmlSerializer ser = new XmlSerializer(typeof(elementB));
            StringBuilder sb = new StringBuilder();
            using (XmlWriter writer = XmlWriter.Create(sb, new XmlWriterSettings() { Indent = true })) 
            {
                ser.Serialize(writer, b);
            }
            Console.WriteLine(sb.ToString());
            elementA a = new elementA();
            a.FirstName = "P";
            a.LastName = "G";
            a.schemaLocation = "http://tempuri.org/XMLSchema.xsd me";
            ser = new XmlSerializer(typeof(elementA));
            sb = new StringBuilder();
            using (XmlWriter writer = XmlWriter.Create(sb, new XmlWriterSettings() { Indent = true }))
            {
                ser.Serialize(writer, a);
            }
            Console.WriteLine(sb.ToString());
        }
    }
}
[System.SerializableAttribute()]
[System.Diagnostics.DebuggerStepThroughAttribute()]
[System.ComponentModel.DesignerCategoryAttribute("code")]
[System.Xml.Serialization.XmlTypeAttribute(AnonymousType = true, Namespace = "http://tempuri.org/XMLSchema.xsd")]
[System.Xml.Serialization.XmlRootAttribute(Namespace = "http://tempuri.org/XMLSchema.xsd", ElementName = "elementB", IsNullable = false)]
public partial class elementA : elementB
{
    private string torefField;
    /// <remarks/>
    [System.Xml.Serialization.XmlAttributeAttribute(Form = System.Xml.Schema.XmlSchemaForm.Qualified, Namespace = "http://www.w3.org/2001/XMLSchema-instance")]
    public string schemaLocation
    {
        get
        {
            return this.torefField;
        }
        set
        {
            this.torefField = value;
        }
    }
}
期待される結果を生成します。
<?xml version="1.0" encoding="utf-16"?>
<elementB xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns:xsd="http://www.w3.org/2001/XMLSchema" xmlns="http://tempuri.org/XMLSchema.xsd">
  <FirstName>P</FirstName>
  <LastName>G</LastName>
</elementB>
<?xml version="1.0" encoding="utf-16"?>
<elementB xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns:xsd="http://www.w3.org/2001/XMLSchema" xsi:schemaLocation="http://tempuri.org/XMLSchema.xsd me" xmlns="http://tempuri.org/XMLSchema.xsd">
  <FirstName>Petru</FirstName>
  <LastName>Gardea</LastName>
</elementB>
2 番目の方法は、必要なものを必要な場所に注入するカスタム ライターに依存します (適切なロジックを前提としています)。
カスタム XmlWriter を実装します。
class MyXmlWriter : XmlWriter
{
    XmlWriter _writer;
    bool _docElement = true;
    public string SchemaLocation { get; set; }
    public string NoNamespaceSchemaLocation { get; set; }
    public MyXmlWriter(XmlWriter writer)
    {
        _writer = writer;
    }
    (other methods omitted)
    public override void WriteStartElement(string prefix, string localName, string ns)
    {
        _writer.WriteStartElement(prefix, localName, ns);
        if (_docElement)
        {
            if (!string.IsNullOrEmpty(SchemaLocation))
            {
                _writer.WriteAttributeString("xsi", "schemaLocation", "http://www.w3.org/2001/XMLSchema-instance", SchemaLocation);
            }
            if (!string.IsNullOrEmpty(NoNamespaceSchemaLocation))
            {
                _writer.WriteAttributeString("xsi", "noNamesapceSchemaLocation", "http://www.w3.org/2001/XMLSchema-instance", NoNamespaceSchemaLocation);
            }
            _docElement = false;
        }
    }
    (other methods omitted)
}
変更されたテスト プログラム:
static void Main(string[] args)
{
    elementB b = new elementB();
    b.FirstName = "P";
    b.LastName = "G";
    XmlSerializer ser = new XmlSerializer(typeof(elementB));
    StringBuilder sb = new StringBuilder();
    using (XmlWriter writer = XmlWriter.Create(sb, new XmlWriterSettings() { Indent = true })) 
    {
        ser.Serialize(writer, b);
    }
    Console.WriteLine(sb.ToString());
    sb = new StringBuilder();
    using (XmlWriter writer = XmlWriter.Create(sb, new XmlWriterSettings() { Indent = true }))
    {
        MyXmlWriter newWriter = new MyXmlWriter(writer) { SchemaLocation = "http://tempuri.org/XMLSchema.xsd me" };
        ser.Serialize(newWriter, b);
    }
    Console.WriteLine(sb.ToString());
}
結果は同じ...
<?xml version="1.0" encoding="utf-16"?>
<elementB xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns:xsd="http://www.w3.org/2001/XMLSchema" xmlns="http://tempuri.org/XMLSchema.xsd">
  <FirstName>P</FirstName>
  <LastName>G</LastName>
</elementB>
<?xml version="1.0" encoding="utf-16"?>
<elementB xsi:schemaLocation="http://tempuri.org/XMLSchema.xsd me" xmlns:xsd="http://www.w3.org/2001/XMLSchema" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns="http://tempuri.org/XMLSchema.xsd">
  <FirstName>P</FirstName>
  <LastName>G</LastName>
</elementB>