I'm pretty sure mine was EDGE. It looked cool and I like puzzle games so I gave it a go.
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Original Portal just a couple days after release. I bought the Half-Life 2 Holiday pack at the store which came with HL2, episode 1, and I think the Source games.
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I registered my original Half Life key on Steam when Steam first came out.
I looked it up and it shows up on my Steam Account Details as this: Half-Life Platinum Pack (Complimentary). I registered a few other boxed purchases on Steam in the intervening years, such as the 2006 Holiday Collection and X3: Reunion.
My first actual purchase from the Steam storefront appears to be Counter-Strike: Global Offensive last year.
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Call of Duty: Black Ops. When I got it I didn't know what Steam was but I was forced to donwload it to play the game. After a while I got bored and downloaded TF2 and played it than I started purchasing games off of steam. Blakc ops isn't in my account becuase I shared the account with my brother back then.
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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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