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If I pick a XeTeX generated PDF with text containing ligatures and open it on a PDF viewer (I use Okular), select some text, copy and paste on Writer, the ligatures are copied without problems, but that's because the original document uses OpenType fonts. If the PDF was generated using LaTeX and metafont, conversion would not be that easy.

Generally speaking, converting PDF to anything is a bad idea, so you need to either translate the original .tex file to .odt as suggested by @David or recreate the whole document from scratch on Writer: any other option would be too much work.