Fluorescent photonic crystal films composed of monodisperse NaYF4:15Yb,0.5Tm@SiO2 (where 15 and 0.5 represent the mole percentage of reactants) core-shell spheres were successfully fabricated and applied in photocatalysis. The core-shell spheres were prepared using a modified Stober method, and fluorescent photonic crystal films were fabricated via a simple self-assembly method. The morphologies, structures and upconversion fluorescent properties of the fluorescent photonic crystal films with different photonic band gaps were characterized. Moreover, their photocatalytic capability in decomposing rhodamine B using near-infrared light was studied. Results indicate that the band edge effect plays a critical role in the enhancement of short wave emission intensity of fluorescent photonic crystal films. Specifically, in comparison to the reference sample without a band edge effect, the 363 nm emission intensity was enhanced by 5.97 times, while the percentage of UV upconversion emission was improved by 6.23%. In addition, the 451 nm emission intensity was enhanced by 5.81 times, and the percentage of visible upconversion emission was improved by 8.88%. Furthermore, fluorescent photonic crystal films with enhanced short wave emission exhibited great photocatalytic performance in the degradation of rhodamine B aqueous solutions under near-infrared light.