Using OpenOffice with 10.04 I was able to print to a Postscript file, but I find I can't do this with LibreOffice and 12.04 - print-to-file goes to PDF.
I want this feature so that I can use a FinePrint-like tool called fprint to print .PS files in booklet form.
When I print from other applications I'm offered the usual choice of printers, including print to .PS, but LibreOffice restricts my choice.
11 Answer
I eventually came cross the solution by accident, but it is also dealt with at the URL given by nomnex (was above, now below!).
File=>Print: Select PDF Choose Options Tab: Select Print To File Press "Print To File" button, select the destination directory, and enter the filename. It seems that the only option here is to print to .PS format.