I think a lot of labels, at least the less-mainstream ones, tend to put up a few mp3s for each artist. I think a good number of you are familiar with SubPop (Iron & Wine, The Gutter Twins, Sleater-Kinney, The Postal Service, etc). Bloodshot Records, for the most part, is an alt. country, rockabilly, roots rock label featuring The Detroit Cobras, Neko Case, Ryan Adams, Old 97s, The Bottle Rockets, etc. Some of the artists aren't currently on the label, but the site still has their older albums up with a lot of mp3 offerings.
Drive-By Truckers have some free songs up on their media page.
Although, they aren't mp3s, last.fm has some full, streaming songs (and in some cases full albums) to listen to for free and the number of full songs seems to get bigger every day. I believe there is a 3 play limit on each song, so be warned. In some instances there are free mp3s as well, though I haven't run into a lot:
Dan Sartain - Join Dan Sartain
HorrorPops - Bring it On
Southern Culture on the Skids Dirt Track Date
SCOTS - For Lovers Only
The Raconteurs - Consolers of the Lonely
Reverend Horton Heat - Smoke Em If You Got Em

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