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[Aldourien]

I've just recently tried out the Dolphin and Dolwin emulators to play Metal Gear Solid: TTS and both couldn't launch it.
The Dolwin couldn't launch because of an error saying this after 0.09s boot time:

Title: Dolwin Hardware Not Implemented
Reason: unhandled HW access : W8 7F000000 = FE (pc:800051B8)

And then the grey background changes back to the file selection lobby.

Computer specs: Windows XP Professional SP3, Intel Core2 Quad CPU Q8200 at 2,33GHz, 2.0GB RAM and ATI Radeon HD 4800 Series.

What am I missing?

[Agozer]

You are missing the fact that Dolwin doesn't really emulate much of anything, let alone Twin Snakes. Your best bet is the latest SVN releases of Dolphin.