Display omitted •Facile electrodeposition of Nickel and Polydiphenylamine on Fluorine tin-doped electrode.•Synergistic effect between Nickel and PDPA enhanced methanol and ethanol electrooxidation.•Rct value of Ni/PDPA is relatively lower than PDPA alone, indicating lower charge resistance.•Enhanced stability of Ni/PDPA compared to PDPA.•Ni/PDPA is highly cost-effective compared to platinized electrode material for DAFCs. Methanol and ethanol oxidation in fuel cells is considered an alternative effective renewable energy. In this work, we investigated the electrooxidation of methanol and ethanol using a novel nanohybrid material consisting of polydiphenylamine (PDPA) and nickel (Ni) nanoparticles onto fluoride doped tin oxide (FTO) electrode using a facile electrodeposition method. The fabricated electrode was well-characterized using X-ray diffraction, field-emission scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy techniques, and Fourier-transform infrared spectroscopy to confirm Ni/PDPA formation. Electrochemical measurements were carried out in 0.1 M KOH, and Ni/PDPA demonstrated excellent electrocatalytic activity due to synergistic effect owing to relatively lower onset potential by Ni and high conductivity of the conductive polymer. In addition, Ni/PDPA catalysts exhibited high current density, relatively low Rct value, and better stability. Based on the obtained electrochemical results, it is confirmed that Ni/PDPA catalysts synthesized via electrodeposition are time-saving, economically viable, and suitable for fuel cell applications, particularly in direct alcohol fuel cells.