•Two different solvents (toluene and chloroform) were used to prepare Langmuir films of PS-b-P4VP(DO13) copolymers.•For toluene, which is a selective solvent for one of the blocks of the copolymer, a higher film-forming ability was observed.•A pronounced effect on the optical storage capability of LS and LB films was observed.•Higher photoinduced birefringence for the films prepared with toluene was developed.•The enhanced properties in toluene are ascribed to the formation of micelles. Langmuir films of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) with an azo dye, 4-4-(phenylazo)-1-naphthylazophenol (Disperse Orange 13, DO13), hydrogen-bonded to the pyridine group of P4VP blocks were investigated. The surface pressure isotherms were considerably different for the copolymer dissolved in a nonselective (chloroform) and selective (toluene) solvents. The Langmuir–Blodgett (LB) and Langmuir–Schaefer (LS) films produced with PS-b-P4VP(DO13) copolymers displayed higher optically induced birefringence than the cast films owing to their nanostructured nature. The photoinduced birefringence properties were particularly enhanced when toluene was used owing to the confinement of azo chromophores in micelles consisting of a P4VP core and a PS corona.