In general, other DD's will say that the DRM is Steamworks or that you need a Steam account to activate the game. In those cases, they're usually safe to buy.
Otherwise, search google for your digital distributor in question, along with "activate on steam" and (for a lot of them) you'll come to a thread on the steam forums with lists of what games activate on steam after being purchased elsewhere (these are not always up-to-date; if the DD page says "Steamworks" or "requires Steam account" trust them! - If they lie, you can complain to customer service)
As a side note, you can check out e.g. cheapshark.com (I think) and several other, similar, sites which look at DD sites and finds the cheapest prices (and most of them you can check that you only want to see steamworks games).
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Just try'n to figure this out. So If i set up a gamersgate account to buy chivalry since its 33% off could i just see what my CD Key is and use it in steam its a game i really want to get but don't think the wife will go for the full $30 a.t.m
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