Try code below.  I had to change 1st line from standalone="true" to standalone="yes"
using System.Linq;
using System.Text;
using System.Xml;
using System.Xml.Serialization;
using System.IO;
namespace ConsoleApplication1
{
    class Program
    {
        const string FILENAME = @"c:\temp\test.xml";
        static void Main(string[] args)
        {
            string file = File.ReadAllText(FILENAME);
            file = file.Replace("standalone=\"true\"", "standalone=\"yes\"");
            StringReader reader = new StringReader(file);
            XmlSerializer xs = new XmlSerializer(typeof(MemberList));
            MemberList  members = (MemberList)xs.Deserialize(reader);
        }
    }
    [XmlRoot("memberList")]
    public class MemberList
    {
        [XmlElement("groupID64")]
        public string groupID64 { get; set;}
        [XmlElement("groupDetails")] 
        public GroupDetails groupDetails { get; set;} 
        [XmlElement("nextPageLink")]
        public Text nextPageLink { get; set; }
        [XmlElement("members")]
        public Members members { get; set; }
    }
    [XmlRoot("groupDetails")]
    public class GroupDetails
    {
        [XmlElement("groupName")]
        public Text groupName { get; set; }
        [XmlElement("groupURL")]
        public Text groupURL { get; set; }
        [XmlElement("headline")]
        public Text headline { get; set; }
        [XmlElement("summary")]
        public Text summary { get; set; }
        [XmlElement("avatarIcon")]
        public Text avatarIcon { get; set; }
        [XmlElement("avatarMedium")]
        public Text avatarMedium { get; set; }
        [XmlElement("avatarFull")]
        public Text avatarFull { get; set; }
        [XmlElement("memberCount")]
        public int memberCount { get; set; }
        [XmlElement("membersInChat")]
        public int membersInChat { get; set; }
        [XmlElement("membersInGame")]
        public int membersInGame { get; set; }
        [XmlElement("membersOnline")]
        public int membersOnline { get; set; }
    }
    public class Text
    {
        [XmlText]
        public string text { get; set;}
    }
    [XmlRoot("members")]
    public class Members
    {
        [XmlElement("steamID64")]
        public List<string> steamID64 { get; set;}
    }
}
Simple solution to get the steamID64 and fix the error in the XML
using System;
using System.Collections.Generic;
using System.Linq;
using System.Text;
using System.Xml;
using System.Xml.Linq;
using System.IO;
namespace ConsoleApplication1
{
    class Program
    {
        const string FILENAME = @"c:\temp\test.xml";
        static void Main(string[] args)
        {
            string file = File.ReadAllText(FILENAME);
            file = file.Replace("standalone=\"true\"", "standalone=\"yes\"");
            XDocument doc = XDocument.Parse(file);
            List<string> steamID64 = doc.Descendants("steamID64").Select(x => (string)x).ToList();
        }
    }
}