The microbial fuel cell is a new kind of green power generation technology. In this paper, the graphene oxide was reduced with hydrazine hydrate at a constant temperature. And the composite anode material of reduced graphene oxide and capacitive polyaniline was used to construct the microbial fuel cell, which had the simultaneous function of power generation and energy storage. The experimental results showed that the power density of the microbial fuel cell comprising the carbon felt/reduced graphene oxide/polyaniline anode was 2.19 times higher than that of the carbon felt/polyaniline anode. In the charging 30 min-discharging 30 min test, the stored charge by the carbon felt/reduced graphene oxide/polyaniline anode was 675.44 C/m2, 5.42 times that of the control anode (124.55 C/m2). In the high throughput test, the surface of the carbon felt/reduced graphene oxide/polyaniline modified anode was 1.75 times higher than that of the control anode. The reduced graphene oxide/polyaniline capacitive composite biological anode material prepared here had the advantages to simultaneously generate electricity and store energy. This paper is expected to break through the current performance bottleneck of microbial fuel cells and improve their performance in energy conversion efficiency and stability.