A bug in XFCE prevents mapping either Space or Escape. This was assigned to xfwm4 (the window manager, which has its own keyboard shortcuts), xfwm4#18 – Cannot use Space or Esc in shortcuts on the presumption that this relates to overlapping keyboard combinations. Ubuntu bug 454337 was closed when they could not reproduce it in 2012 (XFCE 4.8). The upstream xfwm4 bug is still opened, albeit with no notable activity since 2010.
The xfwm4 bug has the following workaround (which works for Super+Space but does not properly implement my preferred Primary+Super+Space sequence). The GUI doesn't let you assign this shortcut, but the command line does:
xfconf-query -c xfce4-keyboard-shortcuts -np \
"/commands/custom/<Super>space" -t string -s "xeyes"
(This uses xeyes
as a stand-in for the program you want to launch.)
You can edit ~/.config/xfce4/xfconf/xfce-perchannel-xml/xfce4-keyboard-shortcuts.xml
directly, though I'd recommend the CLI command instead.
(If relevant: I am not using xfwm4. I use a different window manager.)