EF Code First - 1-to-1 Optional Relationship

One solution would be;

public class User
{
    [Key]
    public string Username { get; set; }

    public virtual Contact Contact { get; set; }
}

public class Contact
{
    [Key]
    public int ID { get; set; }
    public string Name { get; set; }

    public virtual User User { get; set; }
}

        modelBuilder.Entity<User>()
            .HasOptional<Contact>(u => u.Contact)
            .WithOptionalDependent(c => c.User).Map(p => p.MapKey("ContactID"));

You set only your navigational objects in your POCOs and instead you use fluent API to map your key to the correct column.