The influence of Triton X-100 in enhancing the capacitance of polyaniline-based nickel electrodes is reported. Cyclic voltammetric experiments, galvanostatic charge–discharge studies and impedance analysis were carried out in order to investigate the applicability of the system as an electrochemical supercapacitor. A qualitative interpretation of the enhancement is provided. Fourier transform infrared (FTIR), X-ray diffraction and scanning electron microscopy techniques were employed for characterization of the electrode.