I've used the following:
- Git - Little user experience, but see PikiWiki for an unusual Git application.
- Subversion - Helped setting up DevelerCompany's main repository comprising several projects.
- CVS - Managed large project repositories at DevelerCompany and SiriusCompany.
- RCS - Managed large software repositories at SeacCompany.
- Rational Clearcase - I got a degree from "Rational University" for this one. Not joking.
- Source Safe - Listed here because some people think it's a real VCS.