As Jacob points out, while they may appear the same, they are different things.  In fact, there's a significant difference in the way that they handle sending actions to the main thread if you're already running on the main thread.  
I ran into this recently, where I had a common method that sometimes was run from something on the main thread, sometimes not.  In order to protect certain UI updates, I had been using -performSelectorOnMainThread: for them with no problems.
When I switched over to using dispatch_sync on the main queue, the application would deadlock whenever this method was run on the main queue.  Reading the documentation on dispatch_sync, we see:
Calling this function and targeting
  the current queue results in deadlock.
where for -performSelectorOnMainThread: we see 
wait
A Boolean that specifies whether the
  current thread blocks until after the
  specified selector is performed on the
  receiver on the main thread. Specify
  YES to block this thread; otherwise,
  specify NO to have this method return
  immediately.
If the current thread is also the main
  thread, and you specify YES for this
  parameter, the message is delivered
  and processed immediately.
I still prefer the elegance of GCD, the better compile-time checking it provides, and its greater flexibility regarding arguments, etc., so I made this little helper function to prevent deadlocks:
void runOnMainQueueWithoutDeadlocking(void (^block)(void))
{
    if ([NSThread isMainThread])
    {
        block();
    }
    else
    {
        dispatch_sync(dispatch_get_main_queue(), block);
    }
}
Update: In response to Dave Dribin pointing out the caveats section ondispatch_get_current_queue(), I've changed to using [NSThread isMainThread] in the above code.
I then use 
runOnMainQueueWithoutDeadlocking(^{
    //Do stuff
});
to perform the actions I need to secure on the main thread, without worrying about what thread the original method was executed on.