Racemic phosphines are converted into enantioenriched phosphine oxides via a synthetically simple, but theoretically interesting, oxidation procedure in good enantiomeric excess (up to 80%) and excellent yields (> 95%). These phosphine oxides can be oxidatively coupled to provide easy access to enantiopure DiPAMPO analogues. Particularly attractive aspects of this procedure are the operational simplicity and the low cost required to synthesize these high value compounds.