We propose a novel and facile synthesis approach to a porous carbon/graphene composite. Graphene is obtained from room-temperature expanded graphite (RTEG), not involving the use of graphite oxide (GO). Porous carbon is acquired by carbonization and KOH-activation of polyvinylpyrrolidone (PVP), which is used to exfoliate RTEG into graphene and inhibit the restacking of the resultant graphene in the present work. The prepared porous carbon/graphene composite has a high specific surface area (SSA) (3008 m2 g-1) and a hierarchical micro- and meso- pore structure (dominant pores in the range of 1-5 nm). Electrochemical measurement demonstrates that the as-prepared porous carbon/graphene composite can deliver an outstanding specific capacitance of up to 340 F g-1 at 5 mV s-1 in 6 M KOH electrolyte. This specific capacitance is among the highest reported so far for porous carbon/graphene materials. Moreover, the prepared composite as an electrode material also exhibits excellent cycling stability (94.4% capacitance retention over 10 000 cycles). The as-fabricated symmetrical supercapacitor exhibits a high energy density of 10.9 W h kg-1 (based on total mass of electrode materials) and an outstanding energy density retention, even at high power density. Compared with conventional preparation routes for porous carbon/graphene composites, the present approach is significantly simple, convenient and cost-effective, which will make it more competent in the development of electrode materials for high-performance supercapacitors.