All shortcuts--even the two provided by default--assigned via the "Application Shortcut" dialog do not function. Attached is my xfce4-keyboard-shortcuts.xml.
Created attachment 2154 xfce4-keyboard-shortcuts.xml
Are you sure the xfce4-settings-helper is running?
That did the trick. Would this then be an issue with xfce4-session? I start xfce via startxfce4.
There should be an entry in autostart that starts it up for the first time, after which it should get added to the session if you saver your session (at which time the autostart entry gets disabled).
Please don't touch target milestone if you don't know what it's for...
Closing, this is not really a bug as a component was not running.