When you go in the options and click on libreOffice and then on Path and you edit the Temp File in that way that you use the Temp File of LibreOffice on the USB-Stick, everything is ok. But if you close LibreOffice and restart it and verify the Path of the Temporary file it is again on C. In portable OpenOffice 2.4.0 for example, it does not switch after the restart to C.