[en] 5, 7, 12, 14-pentacenetetrone (PT), polycyclic quinone derivatives, are rich in carbonyl, which were investigated as a novel organic electrode material for supercapacitors. PT with a π conjugated system, is a flat molecule, generating strong π–π interactions between molecules. PT molecules were uniformly fixed on conductive reduced graphene oxide (rGO) through π–π interaction by one-step solvothermal method, forming a three-dimensional cross-linked PT@rGO hydrogel. This composite structure was conducive to reducing the charge transfer resistance and promoting the Faraday reaction of electrode, which achieved the superposition of electric double-layer capacitance and pseudocapacitance. Appropriate organic molecular loading can effectively improve electrochemical performance. The optimal PT@rGO electrode material displayed the specific capacitance of 433.2 F g⁻¹ at 5 mV s⁻¹ with an excellent rate capability in 1 mol l⁻¹ H₂SO₄ electrolyte. Finally, the fully pseudocapacitive asymmetric supercapacitor has been assembled by using PT@rGO as positive electrode and benz[a]anthracene-7,12-quinone (BAQ) modified rGO(BAQ/rGO)as negative electrode, which exhibited the good energy storage performance in a cell voltage of 1.8 V. (paper)