<p>The principal goal of the current study is to develop economical, effective and resilient catalysts for water electrolysis to support clean energy production. This study successfully synthesized Mo-doped CaFeO₃ via a simple hydrothermal procedure and thoroughly assessed its catalytic behaviour for the hydrogen evolution reaction (HER) in basic medium. The physicochemical characteristics and morphological features of the electrocatalyst were examined using several analytical techniques. The electrocatalytic efficiency of CaFeO₃ was properly examined by using molybdenum as a dopant to assess its influence on catalytic activity. Additionally, the electrochemical capability of the electrode was investigated in alkaline media using nickel foam (NF) to serve as charge-conducting medium, assessing reaction kinetics, active site availability, electrical conductivity and endurance of Mo-doped CaFeO₃. The electrochemical study of Mo-doped CaFeO₃ demonstrated exceptional performance for HER, having a lowered overpotential of 127 mV, reduced Tafel value of 66 mV dec^− 1 at current density (− 10&#xa0;mA cm^− 2) and exhibits long-term stability for 50&#xa0;h. Additionally, Mo doping in CaFeO₃ improves electrical conductivity and electrochemical efficiency by establishing multiple valence states and oxygen vacancies. This leads to enhanced charge transport and more active sites. However, excessive doping may lead to lattice distortion and secondary phase development, reducing performance and emphasizing the need for optimal dopant concentration.</p>