Metallomicellar catalysis has gained increasing attention in recent years since it made water-incompatible organometallic catalysis highly efficient in water. However, a convenient approach to combine activity and recovery of metallomicelles from aqueous systems has remained challenging to date. Herein, we developed a series of nitrospiropyran-containing metallomicelles which possessed visible-light-responsivity, to realize the visible-light-controlled reaction and separation for asymmetric sulfoxidation in water. A series of nitrospiropyran-containing diblock chiral salen TiIV copolymers were thus prepared by copolymerizing photosensitive nitrospiropyran derivative with hydrophobic chiral salen TiIV monomer via free-radical polymerization. Characterization results suggested their visible-light-controlled self-assembly behavior in water due to the negative photochromism of nitrospiropyran block. The resultant light-responsive metallomicelles induced a micellar catalysis approach in the dark for asymmetric...