Not that I know of.
Steam stopped officially supporting Windows XP awhile back. If Steam were to get more feature like Big Picture Mode it won't work on XP.
Edit: Just ignore what other people are saying. Big Picture Mode works on any resolution.
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games and gameplay is the same with or without it, its the steam user interface that changes
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Setting your monitor to 1280 x 1024 can cause a DDoS attack.
Just sayin'...
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Maybe you can allocate some space and install Windows 7 into your pc while keeping XP
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