There are a number of theories as to why the 33 is on there, but no concrete answer as to why it is.
www.snopes.com (this lists many possible answers as to what the reason is.)
The family of James Tito, one-time chief executive officer of Latrobe Brewing (makers of Rolling Rock beer) owned the brewery from the end of Prohibition until the company was sold in 1987. Based on notes and discussions with family members now dead, James Tito believes the mysterious '33' got there by accident when family members couldn't agree on the wording of a slogan to be printed on the bottle, or even whether the slogan should be long or short. Someone eventually came up with the 33-word pledge now in use, and to emphasize its brevity, he drew a large '33' on the paper. The printer to whom this wording was sent mistakenly thought the '33' was part of the copy and included it on the labels. By the time the mistake was discovered, so many labels had been printed and affixed to bottles that it would have been prohibitively expensive to scrap and replace them, therefore the mistake was retained as a permanent feature of the label. Thus every Rolling Rock bottle now sports the following pledge:
Rolling Rock. From the glass lined tanks of Old Latrobe we tender this premium beer for your enjoyment, as a tribute to your good taste. It comes from the mountain springs to you. "33"
The "mistake" explanation doesn't sound terribly convincing since the printer who sets and runs off thousands of labels before providing the customer with a proof copy to approve does so at his own risk. And even if someone from Rolling Rock had mistakenly approved the label design, error and all, there was no good reason why the errant '33' couldn't have been removed from the copy before the next printing. So, the only real answer here is that no one knows the real answer. And perhaps that is the answer — after all, nothing helps sell a product like a little mystery.