Easy fix via http://ubuntuforums.org/archive/index.php/t-1771058.html
Open file
~/.config/xfce4/xfconf/xfce-perchannel-xml/xfce4-keyboard-shortcuts.xml
find the line
<property name="<Super>Tab" type="string" value="switch_window_key"/>
and change it to
<property name="<Super>Tab" type="empty"/>
Or in terminal (via http://blog.zerosum42.com/2011/10/tech-fixing-tab-key-in-vnc.html):
xfconf-query -c xfce4-keyboard-shortcuts -p /xfwm4/custom/''Tab -r