In order to overcome the shortcomings of the existing photonic crystal solution with low solid content and complex and numerous processes in the preparation of thin films, the simple preparation of large-area solve-responsive photonic crystal films is achieved to meet the requirements of industrial production. Styrene (St), n-butyl acrylate (BA) and allyl methacrylate (AMA) are used as monomers. The colloidal microspheres P(St-BA-AMA) were prepared by semi-stepwise emulsion polymerization, and then the photonic crystal (PCs) films were prepared by thermal assisted self-assembly. The structural morphologies of P(St-BA-AMA) and PCs films were characterized by FTIR and SEM, and the PCs films were tested by DSC and reflectance spectroscopy. The effects of different P(St-BA-AMA) particle size, film forming temperature and response solvent on the structural color of PCs films were investigated. To explore the application of PCs film in patterned anti-counterfeiting and water-responsive paper preparation. The results showed that P(St-BA-AMA) with an average particle size of 198-306 nm could be prepared by adjusting the amount of seed emulsion, and the particle size of each microsphere was uniform. The structural colors of PCs films with P(St-BA-AMA) particle size from 185 nm to 272 nm were purple, blue, green, orange and red, respectively. The PCs films prepared by 210 nm P(St-BA-AMA) were infiltrated by water, ethanol and acetic acid, and showed structural colors of purple, blue and green, respectively. When the film forming temperature is 40~120 ℃, the periodic arrangement of colloidal microspheres on the surface of PCs film remains unchanged and has its own stability. The structural color response of PCs film to solvent can be applied to patterned anti-counterfeiting and water-responsive paper preparation, which can prevent the problem that the structural color rendering is the same as the background color and the anti-counterfeiting effect is not obvious. PCs film can be repeatedly written and erased. The structural color response of PCs film to solvent is due to the interaction between polar solvent and shell monomer, resulting in refractive index difference between polymer microsphere core layer and shell layer, resulting in bright structural color of originally colorless photonic crystal film.