A practical procedure for catalytic asymmetric synthesis of optically active arylglycine derivatives via optically active α-aminonitriles has been developed. The N-benzhydryl α-arylaminonitrile intermediates were prepared in excellent yield (89–99%) and enantiomeric purity (96 to >98% ee) by enantioselective cyanation of aldimines with TMSCN/ i PrOH in the presence of 2.5mol% of an easily prepared Ti/chiral amino alcohol complex at 0°C, without requiring slow addition of the cyanating agent. The easily racemized α-aminonitrile intermediates were efficiently hydrolyzed by an aqueous HCl/TFA mixture to give the arylglycine derivatives in good yield (60–92%) and moderate to excellent enantiomeric purity (85–98% ee).