Microbial Fuel Cell (MFC) is a novel bioelectrochemical system that catalyzes the oxidation of chemical energy in organic waste and converts it directly into electrical energy through the attachment and growth of electroactive microorganisms on the electrode surface. This technology realizes the synergistic effect of waste treatment and renewable energy production. A CF-NiO-PANI capacitor composite anode was prepared by loading polyaniline on a CF-NiO electrode to improve the capacitance of a CF electrode. The electrochemical characteristics of the composite anode were evaluated using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), and the electrode materials were analyzed comprehensively by scanning electron microscopy (SEM), energy diffusion spectrometer (EDS), and Fourier transform infrared spectroscopy (FTIR). MFC system based on CF-NiO-PANI composite anode showed excellent energy conversion efficiency in potato starch wastewater treatment, and its maximum power density increased to 0.4 W/m³, which was 300% higher than that of the traditional CF anode. In the standard charge–discharge test (C1000/D1000), the charge storage capacity of the composite anode reached 2607.06 C/m², which was higher than that of the CF anode (348.77 C/m²). Microbial community analysis revealed that the CF-NiO-PANI anode surface formed a highly efficient electroactive biofilm dominated by electrogenic bacteria (accounting for 47.01%), confirming its excellent electron transfer ability. The development of this innovative capacitance-catalytic dual-function anode material provides a new technical path for the synergistic optimization of wastewater treatment and energy recovery in MFC systems.