Since you asked I did some experimenting, if you first open something in VLC you can pause, resume and stop, volume up or down, mute and unmute. If you hit next it will move to the next item in the play list. None of the other functions will work. Note this is in windows 7 64 bit. It's possible the mouse mode would let you select an item to play instead of using the actual mouse. Neither me nor my wife has used the mouse mode much, too difficult compared to an actual mouse.
This remote as well as any other MCE remote will work perfectly with vlc because you can choose exactly what each button does within vlc by following the steps below. When editing the hotkey, push the actual button on the remote and then use the mouse to accept the change. IMPORTANT...After you make your changes to the hotkey settings, you must restart vlc for the changes to take effect. This issue vexed me for quite some time.
Any thing you can so with the mouse, you can do with this remote. So yes you can. You can alao assign hot keys to the remote - so if.you want to open vlc with one button push that can be accomplished as well.
NO it does not! I have a digital movie library 700 strong and it works wonderfully, and only with, Windows Media Player. I have tried to use it with VLC, Divx Player, and even Windows Media Player but to no avail. I'm not quite sure how some other reviewer got some of the functions to work, but the end result is that it will not function with all it's capacities with any player other than Windows Media Player. Note I am using Windows 7 64 Bit, but I have used it with Vista and XP as well. The Remote also functions as a Mouse as stated previously. You can navigate your PC from the comfort of your bed or couch (But you still need a keyboard preferably wireless). Hope this answer helps.
This may be one of those "your results might vary" situations, but on my machine, this remote will perform the basic VLC functions listed above. However, if you also have iTunes running -- even minimized -- iTunes will "intercept" the commands, no longer allowing you to perform the basic operations in VLC (without using the mouse pad).