In this study, biosynthesized α-MnO2/NiO NPs and chemically oxidative polyaniline (PANI) were synthesized to form ternary composite anode material for MFC. The synthesized materials were characterized with different materials (UV-Vis, FTIR, XRD, TGA-DTA-DSC, SEM-EDX-Gwyddion, CV, and EIS) to deeply examine their optical, structural, morphological, thermal, roughness, and electrocatalytic properties. The degree of surface roughness for α-MnO2/NiO/PANI was
23.65
±
5.652
nm
. This value was higher than the pure α-MnO2, pure PANI, and even α-MnO2/PANI nanocomposite due to surface modification. The total charge storing performance for bare PGE, α-MnO2/PGE, PANI/PGE, α-MnO2/PANI/PGE, and α-MnO2/NiO/PANI/PGE were 5.291, 17.267, 20.659, 23.258, and 24.456 mC. From this, the charge storing performance formed by α-MnO2/NiO/PANI-modified PGE was highest, indicating that this electrode is best in cycle stability and increases its life cycle during energy conversion time in MFC. This is also supported by its effective surface area, having a value of 0.00984 cm2. From this, it is evidenced that the ternary composite catalyst-modified anode facilitates the fast electrocatalytic activity as observed from its high peak current and lower peak-to-peak potential separation (
Δ
E
p
=
0.216
V
) than other electrodes. Such surface modification helps to store more electrical charge by increasing electrical conductivity during its charge/discharge processing time. In addition, the lower charge transfer resistance property with a value of 788.9 Ω and the fast heterogeneous electron transfer rate of ~2.92 s-1 enable to facilitate glucose oxidation, and this enhances to produce high power output and increase wastewater treatment efficiency. As a result, the bioelectrical activity of α-MnO2/NiO/PANI composite-modified PGE was very effective in producing a maximum power density of 506.96 mW m-2 with COD of 81.92%. The above observations justified that α-MnO2/NiO/PANI/PGE serves as an effective anode material in double-chambered MFC application.