Is it possible to deserialize XML into List?

You can encapsulate the list trivially:

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

[XmlRoot("user_list")]
public class UserList
{
    public UserList() {Items = new List<User>();}
    [XmlElement("user")]
    public List<User> Items {get;set;}
}
public class User
{
    [XmlElement("id")]
    public Int32 Id { get; set; }

    [XmlElement("name")]
    public String Name { get; set; }
}

static class Program
{
    static void Main()
    {
        XmlSerializer ser= new XmlSerializer(typeof(UserList));
        UserList list = new UserList();
        list.Items.Add(new User { Id = 1, Name = "abc"});
        list.Items.Add(new User { Id = 2, Name = "def"});
        list.Items.Add(new User { Id = 3, Name = "ghi"});
        ser.Serialize(Console.Out, list);
    }
}