The resolution of a variety of (±)-P-stereogenic phosphines is achieved by exploiting the Staudingerreaction of a (±)-phosphine with enantiopure (1S,2R)-O-(tert-butyldimethylsilyl)isobornyl-10-sulfonylazide. The resulting mixtures of diastereomeric phosphinimines are generally separable by fractionalcrystallization or flash chromatography. Subsequent acid-catalyzed hydrolysis provides thecorresponding optically pure phosphine oxides in high yields.