Quicktime and VLC are able to do this: When you select a movie
and click "open with..." and then define either of them as default
player, every movie of the same type are from now on opened
with it. Since I use Mplayer for almost every movie type, that
would be a great feature.
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I don't think so, unless you can choose your app. MPlayer is
a command line application, not something that actually
hides out in Applications in a .app file.