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Well, there are possible reasons that it may not work out, so the only true answer is to try it for yourself. Download the free trial, see if it works, and, if it gives you an nTitles error, just look for a tutorial.
As a general rule, yes it will. However, as recent help topics and my own experience have shown, some Vista machines just won't play RPG Maker XP. That's why I recommend a free trial, instead of going out and buying it first thing.