I've run into a few gotchas when doing C# XML serialization that I thought I'd share:

• You can't serialize items that are read-only (like KeyValuePairs)
• You can't serialize a generic dictionary. Instead, try this wrapper class (from http://weblogs.asp.net/pwelter34/archive/2006/05/03/444961.aspx):

using System;
using System.Collections.Generic;
using System.Text;
using System.Xml.Serialization;

[XmlRoot("dictionary")]
public class SerializableDictionary<TKey, TValue> : Dictionary<TKey, TValue>, IXmlSerializable
{      
    public System.Xml.Schema.XmlSchema GetSchema()
    {
        return null;
    }

    public void ReadXml(System.Xml.XmlReader reader)
    {
        XmlSerializer keySerializer = new XmlSerializer(typeof(TKey));
        XmlSerializer valueSerializer = new XmlSerializer(typeof(TValue));

        bool wasEmpty = reader.IsEmptyElement;
        reader.Read();

        if (wasEmpty)
            return;

        while (reader.NodeType != System.Xml.XmlNodeType.EndElement)
        {
            reader.ReadStartElement("item");

            reader.ReadStartElement("key");
            TKey key = (TKey)keySerializer.Deserialize(reader);
            reader.ReadEndElement();

            reader.ReadStartElement("value");
            TValue value = (TValue)valueSerializer.Deserialize(reader);
            reader.ReadEndElement();

            this.Add(key, value);

            reader.ReadEndElement();
            reader.MoveToContent();
        }
        reader.ReadEndElement();
    }

    public void WriteXml(System.Xml.XmlWriter writer)
    {
        XmlSerializer keySerializer = new XmlSerializer(typeof(TKey));
        XmlSerializer valueSerializer = new XmlSerializer(typeof(TValue));

        foreach (TKey key in this.Keys)
        {
            writer.WriteStartElement("item");

            writer.WriteStartElement("key");
            keySerializer.Serialize(writer, key);
            writer.WriteEndElement();

            writer.WriteStartElement("value");
            TValue value = this[key];
            valueSerializer.Serialize(writer, value);
            writer.WriteEndElement();

            writer.WriteEndElement();
        }
    }
}

Any other XML gotchas out there?