A novel and simple process for the preparation of enantiomerically pure (S S )-benzenesulfinamide (S S )-3a, (S S )-p-toluenesulfinamide (S S )-3b, (S S )-p-chloro-benzenesulfinamide (S S )-3c and (S S )-p-fluorobenzenesulfinamide (S S )-3d has been developed. The treatment of arylsulfinyl chlorides with (R)-N-benzyl-1-phenylethanamine in the presence of excess triethylamine gave diastereomeric mixtures of N-benzyl-N-(1-phenylethyl)-arylsulfinamides 1, which underwent spontaneous crystallization to furnish diastereomerically pure (R,S S )-N-benzyl-N-(1-phenylethyl)-arylsulfinamides (R,S S )-1a–1d in 28%, 29%, 27% and 31% yields, respectively. The diastereomerically pure compounds (R,S S )-1 were then converted into four enantiopure (R S )-methyl arylsulfinates (R S )-2, and finally into four enantiopure (S S )-arylsulfinamides (S S )-3 in good yields.