The quest for sustainable and clean energy sources has intensified research on the Hydrogen Evolution Reaction (HER) in recent decades. In this study, we present a novel Ce‐doped TiO2 catalyst synthesized through the sol‐gel method, showcasing its potential as a superior electrocatalyst for HER in an acidic medium. Comprehensive characterization through X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), Energy dispersive X‐ray (EDX), and Raman spectroscopy confirms the successful formation of the catalyst. Electrocatalytic performance evaluation, including open circuit potential (OCP), electrochemical impedance spectroscopy (EIS), and Tafel analysis, demonstrates that GCE‐5wt.%CeTiO2 outperforms bare GCE, as well as Ce and TiO2‐based electrodes. Kinetic investigations reveal a Tafel slope of 105 mV dec‐1, indicating the Volmer step as the rate‐determining step. The onset potential for HER at GCE‐5wt.%CeTiO2 is ‐0.16 V vs. RHE, close to the platinum electrode. Notably, the catalyst exhibits a low overpotential of 401 mV to achieve a current density of 10 mA cm−2 with an impressive 95% Faradaic efficiency. Furthermore, the catalyst demonstrates outstanding durability, maintaining a negligible increase in overpotential during a 14‐hour chronoamperometry test. These results have far‐reaching implications for the development of cost‐effective and efficient electrocatalysts for hydrogen production.