The Video settings section shows a green check mark for Vsync, but I've found that the in-game Vsync option has no effect. (You can confirm this by turning on rs_stats
in the console.) TweakGuides agrees; see this page.
TweakGuides also claims, however, that you can force Vsync using your graphics card's control panel, and I was unable to do this using Catalyst Control Center. The option to force Vsync exists but again rs_stats
reveals that it doesn't work.
One solution is D3DOverrider, a tool packaged with RivaTuner, but I'm not sure if there's a good place to download D3DOverrider by itself.