Design of a suitable photoswitchable chiral cation-binding cage for the synthesis of optically active aminals was established using the azobenzene-BINOL hybrid oligoethylene glycol (ABOEG) through / isomerization of the azobenzene unit. Under photoirradiation, both the catalytic activity and enantioselectivity of the generating ()-ABOEG are enhanced, in contrast to that of ()-ABOEG, which can be attributed to the geometrically distinct coordination behavior between the metal cation and the oligoethylene glycols.