Has happened to me four times in many hundreds of Priceline nights. All were at the same hotel about two years ago in quick succession. I really suspect it was a deliberate act on the part of an assistant manager and one employee, who would double bill and then remove the extra in cash.
Bank One (now Chase) was very unhelpful when I challenged the card statement, and refused to delete the charge. While its saved me a fortune Priceline is clueless if anything goes wrong, and in this case I'm not sure what they can do anyway.
I hope you still have a copy of the hotel folio, and I learned to hang onto Priceline printouts till well after the stay bills. I finally got it resolved by taking a later plane next time I was in town and taking the folios and Bank One statements back to the hotel, which may or may not be possible for you. I reguested to see the General Manager, ended up with the new Front End Manager, and was passed to the relevant accountant. (The former manager and accountant first involved were "no longer at the hotel", which was put in context by eye-rolling, so I assumed they were canned). The new accountant was quite competent and it was fixed by the time I flew home.