This work prepared a type of diblock copolymer with thermo- and photosensitivity in ionic liquids (ILs). P(N,N-dimethylacrylamide) (compatible with ILs) was prepared as one segment, while butyl acrylate (BA) and 4-phenylazophenylmethacrylate (AzoMA) were copolymerized as another segment P(AzoMA-r-BA) with stimuli responsiveness. The diblock copolymer showed tunable lower critical micellization temperature (LCMT) in two mixed imidazole ionic liquids. The value of LCMT depends on not only the conformation status of the azo group in copolymers but also the azo group content in copolymers and mixed ratio of ionic liquids. Based on this tunable LCMT, photoinduced micellization/demicellization can be achieved near room temperature by alternate irradiation with visible and ultraviolet light, and it is totally reversible.