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"We’ve also learned that the Steam Box will launch with a version of Linux, which means it will most likely launch with a very small library of games."

http://www.extremetech.com/gaming/145175-gabe-newell-reveals-juicy-steam-box-details-mobile-gaming-project-distaste-for-windows-8

Steam on Linux already has over 50 games, not including Half Life 2, Left 4 Dead 1+2 & Portal 1+2 which are being worked on. There are also Linux versions of almost all Humble Bundle games which I feel safe in assuming most are going through the approval process for release on Steam (the ones that aren't already there).