The preparation of a library of new P-O-P ligands (phosphine-phosphites and phosphine-phosphinites), easily available in two synthetic steps from enantiopure Sharpless epoxy ethers, is reported. The lead catalyst of the series has proven to have outstanding catalytic properties in the rhodium-catalysed asymmetric hydrogenation of a wide variety of functionalised alkenes (16 examples). The excellent performance and modular design of the catalysts makes them attractive for future applications.