Under Windows XP/2000 you can't freely access to port from an user application, you need to use a driver. You can use IO.dll (
http://www.geekhideout.com/iodll.shtml) for that purpose, it is free (for non commercial usage) and it has examples for using it with VB and VC++.
I hope you can use it with C# aswell, unfortunately I don't know too much about this language so I can't tell you how to use it in from a C# application.