The first form will be better indexed by search engines, and is more cache friendly. The latter is both an advantage (you can decrease the load on your server) and a disadvantage (you aren't necessarily aware of people re-visiting your page, and page changes may not propagate immediately to the users: a little care must be taken to achieve this).
The first form also requires (somewhat) heavier processing to get the desired item from the URL.
If you can control the URL syntax, I'd suggest something like:
http://www.example.com/app/servlet/cat1/cat2/item/12345
or better yet, through URL rewrite,
http://www.example.com/cat1/cat2/item/12345
where 12345 is the resource ID. Then when you access the data (which you would have done anyway), are able to do so quickly; and you just verify that the record does match cat1, cat2 and item. Experiment with page cache settings and be sure to send out ETag (maybe based on ID?) and Last-Modified headers, as well as checking If-Modified-Since and If-None-Match header requests.