Porous carbon materials produced by biomass have been widely studied for high performance supercapacitor due to their abundance, low price, and renewable. In this paper, the series of nitrogen-doped hierarchical porous carbon nanospheres (HPCN)/polyaniline (HPCN/PANI) nanocomposites is reported, which is prepared via
in-situ
polymerization. A novel approach with one-step pyrolysis of wheat flour mixed with urea and ZnCl
2
is proposed to prepare the HPCN with surface area of 930 m
2
/g. Ultrathin HPCN pyrolysised at 900°C (~3 nm in thickness) electrode displays a gravimetric capacitance of 168 F/g and remarkable cyclability with losing 5% of the maximum capacitance after 5,000 cycles. The interconnected porous texture permits depositing of well-ordered polyaniline nanorods and allows a fast absorption/desorption of electrolyte. HPCN/PANI with short diffusion pathway possesses high gravimetric capacitance of 783 F/g. It can qualify HPCN/PANI to be used as cathode in assembling asymmetric supercapacitor with HPCN as anode, and which displays an exceptional specific capacitance of 81.2 F/g. Moreover, HPCN/PANI//HPCN device presents excellent cyclability with 88.4% retention of initial capacity over 10,000 cycles. This work will provide a simple and economical protocol to prepare the sustainable biomass materials based electrodes for energy storage applications.