You can create services like this:

Then give the services shortcuts from System Preferences > Keyboard > Shortcuts > Services.
I prefer using third party applications instead of services to assign shortcuts to scripts though. There has been a bug since 10.7 where the shortcuts for services don't always work until you hover over the services menu from the menu bar (or for example run a service once from the menu bar). There is also a noticeable delay before services are run, and the shortcuts for services don't work when an application that doesn't have a services menu (like Tower) is frontmost.
More examples:
tell application "VLC"
if playing then
tell application "System Events" to tell process "VLC"
click menu item "Pause" of menu 1 of menu bar item "Playback" of menu bar 1
end tell
else
play
end if
end tell
tell application "VLC"
set n to 60
if duration of current item - current time > n then
set current time to current time + n
else
next
end if
end tell
tell application "VLC"
set fullscreen mode to not fullscreen mode
end tell
tell application "VLC"
volumeUp
end tell
Open VLC's dictionary in AppleScript Editor to see all supported terminology.