A poly(indole-6-carboxy acid) nanowire composite with β-MnO2 nanorod (6-PICA|β-MnO2[sbnd]NRs) was prepared by an electrochemical method and hydrothermal. The incorporation of β-MnO2[sbnd]NRs and the formation of 6-PICA nanowires are verified by SEM, TEM, Raman, powder XRD, and XPS, where the nanowires perform as an electroactive material and also as an environment to disperse the β-MnO2 nanorods, at different concentrations. The study as a supercapacitor material shows that the specific capacitance of 6-PICA|β-MnO2[sbnd]NRs is 61.35 mFcm−2, higher than that of 6-PICA (43.01 mFcm−2) deposited on the ITO conductive glass electrode. These results indicate that the presence of pure phase β-MnO2 in the form of nanostructure enhances the specific capacitance and ion diffusion in the charge-discharge process of 6-PICA at higher current densities without losing significant stability after 1000 cycles.