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Songler (formerly SpotifyMCE) is a fantastic add-in for Windows Media Center for playing music content from multiple legal streaming music providers - currently Spotify, Last.fm and YouTube. It is the first Add-In for Windows Media Center to play Spotify content, and the most up to date Last.fm Add-In.
It allows both free and premium Spotify subscribers you to play any of Spotify's 6 million tracks instantly, directly from your Media Center, all controlled with your remote. It also allows you to scrobble the tracks that you are playing in Songler to last.fm to build up your music profile, and last.fm subscribers can stream all of their radio stations too.
Open up Media Center. Navigate to Music (Vista) or Extras (Windows 7) and open Songler. In the background, the Spotify app will be launched, playing that track. If you are not in full screen, this will come to the front. If you want to avoid that, run media center in full screen mode with the setting to always keep it at the front. .