Optically pure phosphoroselenoyl chloride was reacted with racemic amines to give phosphoroselenoic amides as two diastereomeric mixtures in high yields. The diastereomeric mixtures were separated by fractional recrystallization or by chromatography. Extrusion of the selenium atom from the separated amides led to diastercomerically pure phosphoramidites. The ability of the obtained amidites to act as optically active ligands was tested in the hydrogenation of an imine.