Abstract: Poly(furfuryl alcohol) (PFA) was synthesized by the hydrothermal method. The effect of surfactant polyvinylpyrrolidone (PVP) amount and hydrothermal duration on the micromorphology of PFA was investigated. PFA and Ni foam were coated with graphene oxide (GO) prepared by the modified Hummers method, and the coating effects of different mass ratios of PFA:GO were investigated. 3D macroporous graphene (3D rGO) was successfully built through removing PFA and Ni foam templates. 3D hierarchical porous graphene (3D PrGO) was constructed on 3D rGO by KOH activation. 3D PrGO/PANI was synthesized by in-situ composite. The phase composition, microstructure and morphology were analyzed by XRD, SEM, TEM, FTIR, XPS and Brunner-Emmet-Teller (BET) measurements. The electrochemical performance of the composites was analyzed by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy. The results show that PFA microspheres with a diameter of about 500 nm are successfully synthesized by controlling the ratio of furfuryl alcohol, PVP and water at 180℃ for 24 h. The coating effect is the best at mass ratio of PFA:GO=1:1. The PFA templates are successfully removed by heat treatment at 450℃ for 6 h and pore sizes of 400-600 nm are formed. The mesopores are formed on the 3D rGO after KOH activation. The specific capacitance of 3D PrGO/PANI composites is 433 F/g at 0.5 A/g, and retains 75% after 1 000 cycling at 1 A/g, which is higher than that of pure PANI (69%).