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Depends on if you are including custom firmwares or not. Vita because if you put custom firmware on it, then you had the entire PS1, PSP and Vita libraries then you could emulate almost every handheld that came before it, aside from like the DS and 3DS because of the two screens.

Standard no modifications, I'd still go with the Vita as you could download some PSP and PS1 games from the PSN store and I enjoyed the Vita games more then I did the PSP, which would be in second place.