My first game on Steam was not a purchase on Steam actually, it was a retail CD-key for the Orange Box: http://puu.sh/6xYng.png
My first purchase on Steam was actually (oddly enough) a gift of Half-life 1 for my little brother-in-law: http://puu.sh/6xY64.png
The first game I bought for me on Steam was about 2 months later and it was a BUNCH of stuff (Heavy Weapon Deluxe, : http://puu.sh/6xXZA.png
Great forum topic :D
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I bought the physical media of Counter-Strike Anthology (which inlcludes CS 1.6 and CS Condition Zero)
It was 2006~2007. I think this was the best purchase I have made on steam, it was the golden age of CS 1.6, played it a lot.
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Team Fortress 2, retail late '08
not long after GarrysMod and several half life 2 titles.
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My first game purchase was Tropico 4. Sadly, I made the mistake of buying the base version instead of the one with all of the DLC. In spite of missing out on some of the extra content, it is a kickass game.
My first f2p purchase on steam was a few weeks before that in the form of G-store coins for Marvel Heroes. It opened up a lot of STASH slots and was used heavily last weekend for the lucky weekend where you got a free hero for a hero purchase and a free costume for a costume purchase. I just about have a full roster now.
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Out of sheer curiosity, what was the first game you've ever bought on Steam?
Mine was Super Meat Boy.
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