You could use String.Last

Code:
Dim Value As String = "123".AppendIfNeeded("}"c)
Console.WriteLine(Value)
Console.WriteLine(Value.AppendIfNeeded("}"c))
Place the following into a code module
Code:
<System.Runtime.CompilerServices.Extension()> _
Public Function AppendIfNeeded(ByVal sender As String, ByVal Character As Char) As String
    Return IIf(sender.Last = Character, sender, String.Concat(sender, Character)).ToString
End Function
Of course you could use the single line in the extension method in your code too.