VLC media player shortcuts:

Audio:

[M] : Mute On/Off

[Ctrl] + [Up arrow] : Turn Volume up

[Ctrl] + [Down arrow] : Turn Volume Down

[Ctrl] + [Up arrow] : Volume Up

[Ctrl] + [Down arrow] : Volume Down

[Ctrl] + [H] : Subtitle Delay Up

[Ctrl] + [J] : Subtitle Delay Down

General Shortcut Keys :

[T] : Show time Played/time left

[Ctrl] + [Q] : Quit program

[F] : Full screen mode

[Ctrl] + [P] : Playlist

[Ctrl] + [M] : Messages

[Ctrl] + [I] : Stream and Media info

[Ctrl] + [A] : Open capture device

[Ctrl] + [W] : Streaming and Transport Wizard

[Ctrl] + [X] / [Ctrl] + [Q] : Exit

[Ctrl] + [V] : VLM control

[Ctrl] + [G] : Extended GUI

[Ctrl] + [B] : Bookmarks

[Ctrl] + [S] : Preferences

[F] : Fullscreen

[+] : Play faster

[-] : Play slower

Video:

[Space] : Play/pause

[S] : Stop

[N] : Next entry in playlist

[F] : Full screen

[Ctrl] + [O] : Quick open file

[Ctrl] + [O] : Open directory

[Ctrl] + [D] : Open disk

[Ctrl] + [N] : Open network stream

[N] : Next item

[P] : Previous item

[Shift] + [Left Arrow] : Very Short Backwards jump

[Shift] + [Right Arrow] : Very Short Forward jump

[Alt] + [Left arrow] : Backwards jump

[Alt] + [Right arrow] : Forward jump

[Ctrl] + [Left arrow] : Medium backwards jump

[Ctrl] + [Right arrow] : Medium forward jump

[Alt] + [Ctrl] + [Left arrow] : Long backwards jump

[Alt] + [Ctrl] + [Right Arrow] : Long Forward jump

[Enter] : Active

DVD:

[Ctrl] + [M] : Go to DVD menu

[Ctrl] + [P] : Selected previous DVD title

[Ctrl] + [F] : Selected next DVD title

[Ctrl] + [U] : Selected previous DVD chapter

[Ctrl] + [D] : Selected Next DVD Chapter

SECOND SET OF SHORTCUTS FROM ANOTHER SOURCE:

VLC is a very versatile media player that can play anything you throw on it, but very so often you really won’t be able to figure out the controls. If you didn’t know, you can get a lot of things done on VLC Player just by using keyboard shortcuts.

Here goes a list of keyboard shortcuts for VLC player:

Space Play/Pause
s Stop
+ Play faster
- Play Slower
t Position
n Next Item
p Previous Item
f Fullscreen
m Mute
Shift+Rt Arrow Forward 3 seconds
Shift+Lt Arrow Backward 3 seconds
Alt+Rt Arrow Forward 10 seconds
Alt+Lt Arrow Backward 10 seconds
Ctrl+q Quit
Ctrl+Up Arrow Volume up
Ctrl+Dn Arrow Volume down
Ctrl+Rt Arrow Forward 1 minute
Ctrl+Lt Arrow Backward 1 minute

Ctrl+r Record
Alt+Ctrl+S Video Snapshot
Ctrl+m DVD Menu
Ctrl+p Select Previous DVD Title
Ctrl+n Select Next DVD Title

Ctrl+B Bookmarks
Ctrl+P Playlist
Ctrl+I Stream, Media Info
Ctrl+S Preferences
Ctrl+G Extended GUI

For your note, all these shortcuts are customizable. You can play with them in the Edit >> Preferences Dialog.

ANOTHER SET OF SHORTCUTS FROM ANOTHER SOURCE:

Shortcuts for navigation while playing movie with VLC for Windows 

Shortcuts to manage VLC Player (Windows version) Playlists and for using some Special Commands

VLC Media Player for Mac Keyboard Shortcuts

Shortcuts for navigation while playing movie with VLC
[CTRL] + [F]    Open folder
[CTRL] + [D]    Open disc menu
[CTRL] + [R] or [CTRL] + [S]    Advanced open file
[CTRL] + [O]    Open single file/files
[CTRL] + [Up Arrow] or [CTRL] + [Down Arrow]    Increase/Decrease Volume
[F]    Switch from/to Fullscreen
[M]    Mute and Unmute Audio
[V]    Show, Switch, or Hide Movie Subtitles
[Space Bar]    Pause or Play the Movie
[P]    Play the Movie (from the very beginning)
[S]    Stop Playing the Movie
[SHIFT] +[Left Arrow] or [SHIFT] + [Right Arrow]    Fast Rewind or Fast Forward by 3 seconds
[ALT] + [Left Arrow] or [ALT] + [Right Arrow]    Fast Rewind or Fast Forward by 10 seconds
[CTRL] + [Left Arrow] or [CTRL] + [Right Arrow]    Fast Rewind or Fast Forward by 1 minute
[ESC]    Exit the Fullscreen mode
[+] or [-]    Play the movie faster or slower
[A]    Change the aspect ratio
[B]    Change Audio/Language track
[C]    Crop screen
[G] or [H]    Increase or Decrease subtitle delay
[J] or [K]    Increase or Decrease audio delay
[Z]    Change Zoom
[CTRL] + [1] or [CTRL] + [2] or [CTRL] + [3] or [CTRL] + [4]    Change the zoom mode
[T]    Show time
[CTRL] + [T]    Go to time
Shortcuts to manage VLC Player, Playlists and for using some Special Commands
[CTRL] + [H]    Hide/Unhide Controls
[CTRL] + [P]    VLC Player Preferences
[CTRL] + [E]    Adjust Audio/Video Effects
[CTRL] + [B]    Edit Bookmarks
[CTRL] + [M]    Open Messages
[CTRL] + [N]    Open Network
[CTRL] + [C]    Open the Capturing Device
[CTRL] + [L]    Open Playlist
[CTRL] + [Y]    Save Playlist
[CTRL] + [I] or [CTRL] + [J]    Media Information
[ALT] + [A]    Audio menu
[ALT] + [H]    Help menu
[ALT] + [M]    Media menu
[ALT] + [P]    Playlist menu
[ALT] + [T]    Tool menu
[ALT] + [V]    Video menu
[ALT] + [L]    Playback menu
[D]    Show the Movie path
[N]    Play Next Movie from Playlist
[F1]    Help
[F11]    Switch Window to/from Fullscreen Mode
[ALT] + [F4]    Quit VLC Media Player

VLC Media Player for Mac users can find most of the keyboard shortcuts by taking a look at the menus. Additional hotkeys are defined in the section “Hotkeys” of your VLC preferences.

Some handy keyboard shortcuts are as follows (courtesy VideoLAN Wiki):

    Press the spacebar to start/pause the video.
    When playing video, holding down the Apple key and pressing the F key enters and exits fullscreen. When in fullscreen you can also use the escape key to exit the fullscreen state.
    When playing video, holding the Apple and Shift keys and pressing the left/right arrow keys, jumps the video backward/forward about a minute.
    When playing video, holding the Apple and Ctrl keys and pressing the left/right arrow keys, jumps the video backward/forward about ten seconds.
    When you are watching a DVD and the video window is the front-most window you can use the arrow keys and the enter key to navigate the DVD menus.
    F – Decrease Audio Delay in milliseconds
    G – Increase Audio Delay in milliseconds
    H – Decrease Subtitle Delay
    J – Increase Subtitle Delay