Excessive usage of fossil fuels has led to significant depletion, creating an energy crisis and environmental concerns. This has prompted the creation of sustainable energy conversion systems. This study explores sol–gel incorporation of Sm‐doped MnTiO3 nanostructure, which exhibits OER activity. Different analytical techniques were used to assess the material's morphology, structure, and textural properties. BET analysis confirmed increased surface area (34 m2 g−1) of Sm‐doped MnTiO3 nanostructure, which enhanced OER performance. The electrochemical results showed that the fabricated doped nanostructure had a lower overpotential of 201 mV, resulting in a current density of roughly 10 mA cm−2 and a Tafel slope of 40 mV dec−1. In EIS analysis, a low Rct value of Sm‐doped MnTiO3 (0.20 Ω) compared with pure MnTiO3 (0.23 Ω) indicates highly efficient charge transfer and a faster faradaic reaction. Chronoamperometry and cyclic stability analyses of Sm‐doped MnTiO3 nanostructure demonstrate stability over 35 h. The fabricated nanostructure has remarkable electrochemical characteristics, making it a promising material for future applications in electrical and other areas.