Step 1:
sudo apt-get remove totem-gstreamer
Step 2:
sudo apt-get install totem-xine totem-mozilla totem
Step 3: Install win64Codecs?
w64codecs_20071007-0.3_amd64.deb
http://www.debian-multimedia.org/pool/main/w/w64codecs/
After install win64Codes.The rmvb video will can be play now.