Cellulose nanocrystals (CNCs), acrylamide (AAm) and poly (ethylene glycol) (PEG) can be co-assembled and photopolymerized into responsive, patterned photonic films with chiral nematic (N*) structures. Here, we report stimuli-responsive CNC/AAm/ PEG composite films (CFs) for use in humidity sensing. With the increase of AAm content, the CFs had an increased helical pitch and showed a red shift. With the adding of PEG, the CFs can quickly capture or release water molecules in air, which resulted in the changes of the helical pitch in N* structures and the structural color. After photopolymerization, the elastic modulus, hardness by nanomechanical testing and tensile strength of polymer films (PFs) were improved compared with CFs. The elastic modulus and hardness of PFs increased with the increase of AAm content. PFs and CFs showed different swelling properties in solutions with different EtOH / H2O ratio. Due to the swelling properties difference between CFs and PFs, partial photopolymerized photonic film showed photonic pattern. This research provides a new method to prepare photonic films with sensitive color response to humidity and photonic pattern, which has potential applications in the fields of sensing, anti-counterfeiting, and decoration.