Hi, I know this is an old thread.
I just had a Polo TDI where the lock button worked, the boot button worked, but the unlock not. Scanned the comfort module, checked and reprogrammed the keys, no luck.
Then I put a new battery in, no luck.
Then I shorted the + and - battery terminals on the pcb inside the keyfob (battery removed please!), put the old battery in, and it worked. Same for the second remote. Happy client! After he had a frustrating and potentially expensive trip to the dealers - they wanted to sell him new keys - okay, it probably would have solved the issue too...
I suspect a latched-up condition occured inside both keyfobs.