Codecs and containers
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If you find that you cannot play common audio (such as MP3) or video files, you might not have the correct codecs installed to play them. Media players using the gstreamer backend (such as Totem) will be able to play most multimedia files after installing these codecs:
pacman -S gstreamer0.10-bad gstreamer0.10-bad-plugins gstreamer0.10-good gstreamer0.10-good-plugins gstreamer0.10-ugly
pacman -S gstreamer0.10-ugly-plugins gstreamer0.10-base gstreamer0.10-base-plugins gstreamer0.10-ffmpeg
Useful media players
You may still find that some files (especially Windows video files) won't play properly in Totem. VLC is a multipurpose media player which has many of its own codecs and can handle the tricky video files, as well as DVD movies with menus.
pacman -S vlc
MPlayer also plays many files. Many times it will play things that won't play in VLC.
pacman -S mplayer
There also is a useful MPlayer plugin to integrate mplayer into browsers, install it with:
pacman -S mplayer-plugin
Install Mplayer binary codecs
As an ultimate solution you can try to install MPlayer binary codecs.
If you are not able to play some files go to http://www.mplayerhq.hu/design7/dload.html, read the instructions and install the codec you need to play your files.
They can also be found in AUR with the name codecs.