When LibreOffice split off from OpenOffice, most of the devs went to LibreOffice. It has made a lot of progress since then. OpenOffice has only released some minor updates since then.
One big difference is that while OpenOffice can open MSO files, LibreOffice compatibility is higher and it can also save to MSO files, both the older (doc, xls) and newer (docx, xlsx) formats.
One big difference is that while OpenOffice can open MSO files, LibreOffice compatibility is higher and it can also save to MSO files, both the older (doc, xls) and newer (docx, xlsx) formats.