It's possible
You can do it by customising your keymap or make some buttons in home screen / programs submenu.
Some examples:
System.Exec(C:\Progra~1\Intern~1\iexplore.exe)
System.Exec(C:\Progra~1\Mozill~1\Firefox.exe)
System.Exec(C:\Progra~1\Opera\opera.exe)
System.Exec(/usr/bin/firefox)
System.Exec(C:\Progra~1\Barbie~1\Barbie~1\Beauty.exe) starts my daughters favourite game
Set whatever you like but use ~1 because if there is a space in path it won't work.
Don't ask me why, what I do know is that I can't make a skinsetting for setting your favourite games due to the space problem.