Microporous carbons (MPCs) are promising electrode materials for supercapacitors because of their high surface area and accessible pores. However, their low electrical conductivity and mechanical instability result in limited power density and poor cycle life. This work proposes a unique two-layered film made of polyetheretherketone-derived MPCs and reduced graphene oxide (rGO) as an electrode for supercapacitors. Electrochemical characterizations of films show that such a layered structure is more effective in increasing the accessibility of ions to the hydrophilic MPCs and establishing conductive paths through the rGO network than a simple mixed composite film. The two-layered structure increases the capacitance by∼124% (237 F g-1) with excellent cycling stability (∼93% after 6000 cycles). More importantly, we demonstrate that such performance improvements result from an optimal balance between electrical conductivity and ion accessibility, which maximizes the synergistic effects ofMPCand rGO. The MPCs, which are exposed to the surface, provide a highly accessible surface area for ion adsorption. The rGO serves a dual function as a conductive filler to increase the electrical conductivity and as a binder to interconnect individualMPCparticles into a robust and flexible film. These findings provide a rational basis for the design of MPC-based electrodes in high performance supercapacitors.