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.