VLC hotkeys with Ctrl:

Ctrl + Up Arrow : Increase volume
Ctrl + Down Arrow : Decrease volume

Ctrl + A : Advanced controls
Ctrl + B : Bookmarks
Ctrl + C : Open capture device
Ctrl + D : Open disc
Ctrl + E : Extended settings
Ctrl + F : Open Folder/Directory
Ctrl + H : hide/show menus (a.k.a Minimal view; like in Acrobat Reader)
Ctrl + I : Media Information
Ctrl + J : Codecs Information
Ctrl + L : Hide/Show playlist
Ctrl + M : Messages
Ctrl + N : Open network stream
Ctrl + O : Open File
Ctrl + P : Preferences
Ctrl + Q : Quit
Ctrl + R : Convert/Save
Ctrl + S : Streaming
Ctrl + U : Dock/Undock playlist
Ctrl + V : Paste Location/Paste MRL
Ctrl + W : VLM configurator
Ctrl + X : Load playlist
Ctrl + Y : Save playlist
Ctrl + Z : Switch to skins (requires restart)

VLC hotkeys with Shift:

Shift + A : cycle audio device
Shift + R : Record
Shift + S : snapshot

VLC hotkeys with Alt:

Alt + A : audio menu (in English)
Alt + C : crop / (+shift) uncrop bottom
Alt + D : crop / (+shift) uncrop left
Alt + F : crop / (+shift) uncrop right
Alt + H : help menu (in English)
Alt + L : playback menu (in English)
Alt + M : media menu (in English)
Alt + R : crop / (+shift) uncrop top
Alt + T : tools menu (in English)
Alt + V : video menu (in English)

* Don’t miss VLC Untied, a free program that lets you select one or more files or folders in Windows Explorer and load them to VLC media player instantly using a keyboard shortcut, even removing completely any files that may be already loaded and playing.