A polypyrrole–reduced graphite oxide core–shell composite was facilely fabricated through electrostatic interactions and π–π accumulation. This novel composite shows remarkable performance as an electrode material for supercapacitors, with a high specific capacitance of 557 F g⁻¹ at a current density of 0.5 A g⁻¹, and retains a high value after 1000 charge–discharge processes. The maximum energy density of the fabricated supercapacitor based on the mass of active electrodes is calculated to be 49.5 W h kg⁻¹ and 33.3 W h kg⁻¹ at a power density of 0.22 kW kg⁻¹ and 6.06 kW kg⁻¹, the improved capacitance might be mainly ascribed to higher conductivity and more crumpled surface of the composite.