Two kinds of composite films were obtained by incorporating upconversion nanophosphors into monodomain and polydomain crosslinked liquid crystalline polymer films containing azotolane moieties. When exposure to continuous-wave near-infrared light at 980 nm, the monodomain composite film generated fast bending along the rubbing direction of the polyimide alignment layers, whereas the bending direction of the polydomain composite film was random. The anisotropic effect of the azotolane mesogens on the deformation and the measurement of thermal effect indicate that the bending is caused by the means of photochemistry rather than the thermal effect of NIR light; that is, the upconversion luminescence of the nanophosphors leads to trans-cis photoisomerization of the azotolane units and the alignment change of the mesogens.