The NaYF4:Yb3+,Tm3+ upconversion nanoparticles (UCNPs) with blue fluorescence emission were prepared by thermal decomposition method. Then, the core-shell nanoparticles (CSNPs) with enhanced upconversion fluorescence were obtained by epitaxially growing a NaYF4 shell on UCNPs core. In order to realize hydrophilic modification of CSNPs and endow them with pendent polymerizable double bonds, a layer of SiO2 modified with 3-(Trimethoxysilyl) propyl methacrylate (MPS) were coated on CSNPs by reverse microemulsion method. Finally, lanthanide-doped NaYF4/PS composite microspheres were prepared via the emulsion polymerization of styrene in the presence of CSNPs@SiO2-MPS. The upconversion fluorescence photonic crystal (UCPC) film was constructed via the self-assemble of lanthanide-doped NaYF4/PS microspheres through the vertical deposition method. The result showed that the UCPC film could be observed not only in obvious pink structural color at specific angle of daylight, but also the blue fluorescence under 980 nm laser irradiation. The UCPC films with dual-mode optical characteristic could be used to in information encryption, which have broad application prospects in the fields of information protection and packaging anti-counterfeiting.