Confined catalysis under the cover of 2D materials has emerged as a promising approach for achieving highly effective catalysts in various essential reactions. In this work, a porous cover structure is designed to boost the interfacial charge and mass transfer kinetics of 2D-covered catalysts. The improvement in catalytic performance is confirmed by the photoelectrochemical oxidation evolution reaction (OER) on a photoanode based on an n-Si substrate modified with a NiOx thin-film model electrocatalyst covered with a porous graphene (pGr) monolayer. Experimental results demonstrate that the pGr cover enhances the OER kinetics by balancing the charge and mass transfer at the photoanode and electrolyte interface compared to the intrinsic graphene cover and cover-free control samples. Theoretical investigations further corroborate that the pore edges of the pGr cover boost the intrinsic catalytic activity of active sites on NiOx by reducing the reaction overpotential. Furthermore, the optimized pores, which can be easily controlled by plasma bombardment, allow oxygen molecules produced in the OER to pass through without peeling off the pGr cover, thus ensuring the structural stability of the catalyst. This study highlights the significant role of the porous cover structure in 2D-covered catalysts and provides new insight into the design of high-performance catalysts.