You can use bitcoin to make purchases at the following locations:
1. Overstock.com
2. TigerDirect.com
3. Gyft.com (allows you to then purchase stuff from stores that accept gift cards, but not btc)
4. bitcoinshop.us
5. cryptothrift.com (a bitcoin auction site)
You can also browse all the vendors that accept bitcoin through bitpay.com here:
https://bitpay.com/directory#/ (this list is over 20,000 places long)
Also bitcoins are great ways of accepting payment for high risks sells, where the buyer could collect digital goods and then reverse the payment. IE selling serial keys, game currency etc.