Assuming that Member(or something else) is a class, this is simple:
members[0].Country = "England";
You simply update the object referenced by the dictionary. To go through it is equivalent to:
Member member = members[0];
member.Country = "England";
, , , .
, Member , :
Member bob = GetBob();
bob.Country = "England";
Console.WriteLine(members[0].Country);
Member ... , :)