This tutorial is intended to demonstrate how to do this in NOP, which uses the Xfce 4.4 desktop. Specifically QuirkyNOP, but other variants should be the same.
It consists of three steps: discovering the identity of the key as seen by X, binding that identity to a string that Xfce understands, then assigning a command to the key.
So. To begin, open a terminal window menu>utility>terminal, and simply type
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xev
This will bring up a little target box and leave the terminal window open on the desktop. Watch the terminal window, and hit the key you want to use. For this example, we will use the Windows Menu key.
Assuming X can recognise this key, this will bring up a bunch of text in the terminal window. Look for the keycode, usually 115, and make a note of the number.
OK, so now we have the key identity.
Next, we need to bind that identity to a string that Xfce understands.
So. First, create a text file in your root directory called .Xmodmap Note the dot at the start of the file name is important. Leave this (so far) blank file open. Now we need to find a suitable string that Xfce understands. These strings are all held in a text file at /usr/share/X11/XKeysymDB. Open this file and look for a suitable string, in this case its XF86MenuKB.
Then add the entry to .Xmodmap. This is the syntax:
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keycode 115 = XF86MenuKB
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xmodmap .Xmodmap
All that remains now is to tell Xfce to use this key with the command of your choice. In this example, we will set it to launch Firefox.
So. Menu>Settings>Xfce Settings Manager, and launch the keyboard section by clicking the icon. Choose the Application Shotcuts tab. Click the + button to add a command, and use the Open button to find the command you want, in this case, /usr/lib/firefox/firefox, and click OK. That little window will close and another will pop-up asking for the key. Just hit the key you want to use, in this case, the Windows Menu key, and you are done.
From now on, just hitting the Windows Menu key will launch Firefox for you.
You can add as many bindings as you like to .Xmodmap, then run xmodmap .Xmodmap via the terminal to set it, but watch out for creating conflicts.
Good Luck..................