The efficient, long-lasting, and low-cost materials are in great demand as electrocatalysts for energy-related applications in the future for the generation of renewable energy. In this study, CeO x /Cu 2 SiO 4 is hydrothermally fabricated as a promising oxygen evolution reaction (OER) electrocatalyst in which cerium oxide (CeO x ) is decorated on the rough surface of Cu 2 SiO 4 . Various analytical tools were utilized to determine the structural, morphological, and textural properties of the electrocatalyst. The geometrical effect and electrical interactions between the bimetal components are responsible for the outstanding performance of 10% CeO/Cu 2 SiO 4 nanocomposite. The decoration of 10% CeO on the Cu 2 SiO 4 displays the low Tafel slope of 28 mV dec −1 and an overpotential of 470 mV to achieve a current density of 10 mAcm −2 with a high stability of 32 h as compared to pristine Cu 2 SiO 4 and other doped materials. This work manifested that the presence of Ce in 10% CeO/Cu 2 SiO 4 can significantly improve the electrocatalytic performance toward the water-splitting process. Hence, in this study, the CeO decoration on a transition-metal silicate surface opens an innovative avenue for the advancement in the OER electrocatalysts and other energy conversion devices.