Chat will work if both machines have the "chat" option checkmarked.

When you type a message in the bottom of the chat window and hit the return key, a similar message box shows up on the other machine, and if the person sees the message they can type a reply in the bottom of their box. When they hit return, their message will show up in the message box on your machine.

However, many people run limewire and are away from the computer and so they do not notice the chat box, and you may not get a reply.