This is an AppleScript to allow the ability to select a song from a VLC playlist and Add the song to your iTunes Library.

AddiTunesFromVLC.scpt

global songAdded
global selectedSong

# This variable is used as a boolean to see if a file has been added to iTunes or not
set songAdded to false
# This variable is used to store the alias location of the song to be deleted / added
set selectedSong to false

getSong()
addSong(selectedSong)
finishUp()

on getSong()
	# Reveal selected song from the VLC playlist in the Finder
	tell application "VLC"
		activate
		try
			tell application "System Events" to keystroke "r" using {shift down, command down}
		end try
	end tell
	
	# Save the selected song
	if is_active("Finder", true) is true then
		tell application "Finder"
			set selectedSong to (get selection as alias)
		end tell
	end if
end getSong

# Add Song to iTunes Library
on addSong(selectedSong)
	# Bail out if there's no saved selected song
	if selectedSong is not false then
		tell application "iTunes"
			launch
		end tell
		
		if is_running("iTunes", true) is true then
			try
				tell application "iTunes"
					add selectedSong to playlist "Music" of source "Library"
					set songAdded to true
				end tell
			end try
		end if
	end if
end addSong

on finishUp()
	tell application "Finder" to close window 1
	tell application "VLC" to activate
end finishUp

# Utility functions
on is_running(appName, waitBoolean)
	tell application "System Events"
		set appRunning to (name of processes) contains appName
		
		if waitBoolean is true then
			# Wait for the App to start running
			set wait to 0
			repeat until appRunning is true or wait is greater than 8
				set appRunning to (name of processes) contains appName
				set wait to wait + 0.1
				delay 0.1
			end repeat
		end if
		
		return appRunning
	end tell
end is_running

on is_active(appName, waitBoolean)
	tell application "System Events"
		set activeApp to (name of first application process whose frontmost is true) contains appName
		
		if waitBoolean is true then
			# Wait for the App to become active
			set wait to 0
			repeat until activeApp is true or wait is greater than 2
				set activeApp to (name of first application process whose frontmost is true) contains appName
				set wait to wait + 0.1
				delay 0.1
			end repeat
		end if
		
		return activeApp
	end tell
end is_active