My first Steam game was Portal; I first registered on Steam when doing so netted you a free Portal as a perk. My first actual purchase? Wow, that was a long time ago, so it's tricky to remember. I'm 90% sure it was TES IV: Oblivion, which I originally played through not-quite-so-legal channels, loved, and decided to buy. I honestly can't remember for sure, though.
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I am ashamed of how many hours I put into that game
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Tobe's Vertical Adventure at full price because I wanted to add friends and stuff.
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I think the first thing I bought on Steam was Terraria the day it came out, before that I had a couple free to play games, hard to remember though!
How about you guys?
EDIT: So Terraria was actually a gift from a friends account, but I was at his house at the time and I gave him money to buy it, so technically it was my first purchase even though it's listed as a gift, but after that was Magicka
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