PS2 games won't work either at first.
It was unclear if the PlayStation Vita would be compatible with PSone Classics purchases on your PlayStation account, though it was assumed it would be possible given the fact that it would share the same account.Today, the truth is still shrouded, but it was announced that they won't be compatible at least at launch
The Japanese Vita FAQ outlines that at launch, archived releases (PSone, PS2, etc) won't be available, though Sony will have updates on the feature at a later point. As of right now, it's only confirmed that the Vita will be compatible with downloaded PSP games initially. Currently, it is unknown if the American launch of the Vita will feature support for archived releases at this time.
Editor's Note: Thanks to Luke for pointing out the inaccuracy of the article. It has been amended to clarify this is only at launch and that Sony will report details on the capabilities in the future.
This article is a bit incorrect. At launch PS Vita is not compatible with Game Archives (which include stuff like PSone and TurboGrafx 16). Key point is that it's not supported AT LAUNCH and according to Sony's FAQs, Sony will share details later for future support.
http://andriasang.com/comz3m/
The article has been updated to include this information. Thanks Luke.
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