Harnessing multisite proton-coupled electron transfer (PCET) through deprotonation of a photoactive Zr coordination cage unlocks oxidative photocatalysis of strong C─H and O─H bonds. This reactivity overcomes the energetic barrier that renders electron transfer alone inaccessible. The Zr platform acts as an ambipolar mediator that unites oxidative and reductive PCET pathways, each operating through distinct mechanisms, and offers new insights for sustainable solar-to-chemical energy conversion, as reported by Pablo Garrido-Barros et al. in their Communication (e202510723).