Anyway, I agree with the others that while this is nifty it won't always be accurate for everyone. For instance my township is contained within a very, very large county so typically mail is addressed to the specific township rather than the county. I do not know how or if that could even make a difference but our local post office has suggested it.
Overall pretty interesting idea. I think using this plus a way for users to validate the information found it could be useful. The only thing I would be wary of is the website is technically sending a third party the user's information. Your service could then build up information regarding a website's typical customer. Probably not something to worry about but I know most of the places I've worked at they WOULD NOT allow this; they downloaded their own offline zipcode lookups.
EDIT: Perhaps a way to download and get offline updates would be helpful especially if your website went down.