This study explores novel approaches to enhance photocatalysis efficiency by introducing a photonic crystal (PC)-enhanced, multi-layered sub-bandgap photocatalytic reactor. The design aims to effectively utilize sub-bandgap photons that might otherwise go unused. The device consists of three types of layers: (1) two polymeric triplet-triplet annihilation upconversion (TTA-UC) layers converting low-energy green photons (λEx = 532 nm, 2.33 eV) to high-energy blue photons (λEm = 425 nm, 2.92 eV), (2) a platinum-decorated WO3 layer (Eg = 2.8 eV) serving as a visible-light photocatalyst, and (3) a PC layer optimizing both TTA-UC and photocatalysis. The integration of the PC layer resulted in a 1.9-fold increase in UC emission and a 7.9-fold enhancement in hydroxyl radical (•OH) generation, achieved under low-intensity sub-bandgap irradiation (17.6 mW cm–2). Consequently, the combined layered structure of TTA/Pt-WO3/TTA/PC achieved a remarkable 38.8-fold improvement in •OH production, leading to outstanding degradation capability for various organic pollutants (e.g., 4-chlorophenol, bisphenol A, and methylene blue). This multi-layered sub-bandgap photocatalytic structure, which uniquely combines TTA-UC and PC layers, offers valuable insights into designing efficient photocatalytic systems for future solar-driven environmental remediation.