Oxygen evolution reaction (OER) plays a crucial role as a counter half-reaction for both electrochemical hydrogen production through water splitting and the generation of valuable carbon compounds via CO 2 reduction. To overcome the sluggish kinetics of the OER, significant efforts have been devoted to developing cost-effective, sustainable, and efficient electrocatalysts, with transition-metal-based catalysts emerging as promising candidates. Herein, we successfully synthesized a core−shell type nanostructure of Fe-doped CoMoO x /CoMoO x (CMFO), which exhibits excellent electrocatalytic properties for OER. The presence of an amorphous layer of Fe-doped CoMoO x with abundant oxygen vacancies, along with the stability of a key OER intermediate, *O, contributes to the enhanced activity of CMFO catalyst compared to pristine CoMoO x (CMO). The optimized catalyst of CMFO-550 achieved much lower overpotential and Tafel slope and also exhibited better remarkable long-term stability for over 90 h compared to CMO-550. These findings highlight the potential of CMFO-550 as a cost-effective and highly efficient electrocatalyst for the OER. The successful development of this core−shell nanostructure opens up a new opportunity for the design and synthesis of advanced electrocatalysts for the OER, with implications for various applications in energy conversion and storage.