Almost Definitely SVN. SVN sports a different way of working (Copy-Modify-Merge instead of Lock-Modify-Unlock). It's a bit of a learning curve, but it's the way things have gone for several years now, so most devs will have to learn it at some time or other anyway. Lock-Modify-Unlock is way too much of a pain, and there are serious collaboration problems that it actually contributes to, which I'd be happy to explain if you're curious.
Seconding the comments about how bad VSS is as well. Here are various links that cover the topic:
http://www.codinghorror.com/blog/archives/000660.html
http://www.developsense.com/testing/VSSDefects.html
http://wadhome.org/svn_vs_vss.html
Edit: See also:
Source Control - Lock vs. Merge?