Can someone point out the main differences between the two?
It seems that, at least conceptually, the two are very closely related. If I were to hazard a guess, I would say that the publish/subscribe method is a subset of the mediator pattern (since the mediator need not necessarily be used in the publish/subscribe manner, but the latter seems to require a sort of mediator object). Is that anywhere near close to it?
How I would describe the difference is that in mediator you probably care if the end application receives the message. So you use this to guarantee who is receiving the message. Whereas with pub/sub you just publish your message. If there are any subscribers they will get it but you don't care.