I have a silverlight app that uses WCF both by polling Duplex and \"normal\" async calls. everything was working fine, until I added a global.asax file.
There are some types of binding which support accessing asp.net session data, I really dont see how it would affect unless WCF tries to hook into the session_start event just like a http module does. You could also use reflector to disassemble the code where you where getting the exception.