Setting shortcuts in Xfce is not that intuitive, at least for me. I was interesting in using the “home” button in my lenovo S10e’s keyboard. After doing a research a reading carefully I understood how to do it.
1) Go to Applications > Settings > Xfce 4 Setting manager. The following windows will show up:
2) Select the Keyboard icon:
3) Select the second tab. There click on Add button. A small window dialog will pop up:
Fill in the command field with the application you want to launch. In this example a used xfce4-popup-menu to pop the Applications menu up. Click on Ok.
4) Here comes the non-intuitive part. You will see a window dialog, but only the Cancel button will be available. Well, here the window dialog will be waiting for the shortcut you want to assign to the launcher. Press the keyboard shortcut (like the “house” button) and the windows will close by itself.
Now, if you press the “home” button (or the keystroke you selected), the Applications menu will show up. If you want to use another application, just change xfce4-popup-menu with the command you want to use (for instance thunar, gnome-terminal, iceweasel, etc).