Abstract Water oxidation is an important reaction for multiple renewable energy conversion and storage-related devices and technologies. High-performance and stable electrocatalysts for the oxygen evolution reaction (OER) are urgently required. Bimetallic (oxy)hydroxides have been widely used in alkaline OER as electrocatalysts, but their activity is still not satisfactory due to insufficient active sites. In this research, A unique and efficient approach of sacrificial W to prepare CoFe (oxy)hydroxides with abundant active species for OER is presented. Multiple ex situ and operando/in situ characterizations have validated the self-reconstruction of the as-prepared CoFeW sulfides to CoFe (oxy)hydroxides in alkaline OER with synchronous W etching. Experiments and theoretical calculations show that the sacrificial W in this process induces metal cation vacancies, which facilitates the in situ transformation of the intermediate metal hydroxide to CoFe-OOH with more high-valence Co(III), thus creating abundant active species for OER. The Co(III)-rich environment endows the in situ formed CoFe oxyhydroxide with high catalytic activity for OER on a simple flat glassy carbon electrode, outperforming those not treated by the sacrificial W procedure. This research demonstrates the influence of etching W on the electrocatalytic performance, and provides a low-cost means to improve the active sites of the in situ self-reconstructed bimetallic oxyhydroxides for OER.