Deformable liquid crystal polymers (LCPs) driven by more than one external stimulus have received extensive attention in fields ranging from multifunctional soft robots to bionic actuators. Combining responsive liquid crystal with nonmesogenic responsive groups within polymer offers a versatile way to obtain multiresponsive LCPs. However, the incorporation of nonmesogenic responsive groups causes interruption in the assembly of mesogens and brings a challenge to the alignment of LCPs. Herein, a new method is put forward to facilitate uniform mesogen alignment by exerting water vapor in the film preparation process. Using this method, vapor-assisted alignment, the homeotropic alignment of azobenzene mesogens is achieved in a copolymer containing nonmesogenic poly(ethylene glycol) (PEG). The obtained copolymer films present photodeformation brought by azobenzene isomerization and humidity-responsive deformation resulting from the asymmetric swelling of film surfaces. The dual-responsive smart "blinds" and bionic flower actuators are fabricated to demonstrate the integration of the two different stimuli. This work is anticipated to provide a feasible alignment method for multiresponsive LCPs, showing the potential applications in soft robots, sensors, and biomimetic devices.