The photoresponsive behavior of an amphiphilic diblock liquid-crystalline (LC) copolymer (P40A37) was studied in both toluene solution and spin-coated film. The LC copolymer in a film state showed slower response and relaxation than that in the solution. Significant H-aggregation in the film led to a blue shift by 16 nm at the maximum absorption. The photochemical phase transition was observed with a polarizing optical microscope (POM) upon exposure to 366-nm light. The photoinduced isotropic state remained stable at room temperature, indicating the potential application for 2-D and 3-D storage.