If it's not there, right click Steam in your task bar, and choose Big Picture.
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Haven't tried plugging in the old PS2 controller yet, but the layout looks nice enough.
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you gotta update your steam, get the beta-update because there's no button yet in the "stable" version
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it says on the info how to get into big screen
im using my 42" tv with steam and there is no button on top right to activated big screen mods
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