Plasmonic photocatalysis based on metal–semiconductor heterojunctions is considered a key strategy to evade the inherent limitations of poor light harvesting and charge separation of semiconductor photocatalysts. It can be profitably combined with three-dimensional photonic crystals (PCs) that offer an ideal scaffold for loading plasmonic nanoparticles and a unique architecture to intensify photon capture. In this work, Mo-doped BiVO₄ inverse opals were applied as visible light-responsive photonic hosts of Ag and/or Au plasmonic nanoparticles in order to exploit the synergy of plasmonic and photonic amplification effects with interfacial charge transfer for the photoelectrocatalytic degradation of recalcitrant pharmaceutical contaminants under visible light. Photoelectrochemical evaluation indicated a major contribution from hot spot-assisted local field enhancement, most pronounced for Ag/Mo-BiVO₄ PCs due to the spectral overlap of the localized surface plasmon resonance with the electronic absorption and blue-edge slow photon region of Mo-BiVO₄ PCs, in contrast to weak plasmonic sensitization effects for the Au-modified PCs. The diverse band alignment at the metal–semiconductor interfaces resulted in the enhanced photoelectrocatalytic degradation of tetracycline broad spectrum antibiotic by Ag/Mo-BiVO₄ and the refractory ibuprofen drug by (Ag,Au)/Mo-BiVO₄, attributed to the enhanced charge separation by electron transfer toward Ag nanoparticles. Combination of visible light activated semiconductor PCs and plasmonic nanoparticles with suitable band alignment and photonic band gap may provide a versatile approach for the rational design of efficient plasmonic–photonic photoeletrocatalysts.