I used to work at one of those bakery outlets who throw perfectly good food away.
At the store I worked at, we got the bread from the grocery store whos dates would expire in three to four days. We would sell it for a reduced price. The day the date hit, we had to throw it out. We did give some to the local foodbank but often they would say we had more than they could take.
We would have people come in and ask for old bread for their animals. We were happy to give them some. In fact, I think we ended up giving them more than what they ever expected. Trust me, it was easier just to give people that bread than put it on the shelves and then just have to take them off again a day later. Of course the manager at that store didn't care and the people who run the company are out of Los Angles (I am up in Santa Barbara) so we didn't have the BIG bosses come by too often.
We would mostly throw stuff out at closing time so if you are going to go looking for bread, I would say that is the best time to do it. Sometimes I would just leave the bread in a shopping cart by the dumpster and then finsih other stuff up around the store before going back out and throwing it out. I know that there were always people who took advantage of this oppurtunity.