Footwear play a big role in causing bunions and a big role in providing the resistance that makes bunions painful, so going barefoot is going to take those factors away which can only be a good thing.
However, it is not always that practical and the environment is not necessarily conducive to it. It can be a lot easier to do it around the home and on the beach, but not really for going to work! The choice is yours as to just how much you need to or can go barefoot.
There was a fad a while back towards barefoot running that did not last long as too many runners got an injury and it did not live up to the promise of the benefits that those promoting it claimed you would get for it.