The development of earth-abundant photocatalytic assemblies has been one of the bottlenecks for the advancement of scalable water splitting cells. In this study, a ZnCr layered double hydroxide and a CoFe Prussian blue analogue are combined to afford an earth-abundant photocatalytic assembly involving a visible light-absorbing semiconductor (SC) and a water oxidation catalyst (WOC). Compared to bare ZnCr-LDH, the SC-WOC hybrid assembly exhibits a threefold enhancement in photocatalytic activity, which is maintained for 6 h under photocatalytic conditions at pH 7. The band energy diagram was extracted from optical and electrochemical studies to elucidate the origin of the enhanced photocatalytic performance. This study marks a straightforward pathway to develop low-cost and precious metal-free assemblies for visible light-driven water oxidation.