The oxygen evolution reaction (OER) is an ideal model to study the relationship between the activity and the surface properties of catalysts. Defect engineering has been extensively developed to tune the electrocatalytic activity for OER. Compared to the anion vacancies in metal oxides, cation vacancies are more challenging to selectively generate, and the insight into the structure and activity of cation vacancies‐rich catalysts are lacked. Herein, using SnCoFe perovskite hydroxide as a precursor, abundant Sn vacancies on the surface were preferentially produced by Ar plasma. Sn vacancies could be preferentially produced as confirmed by the X‐ray absorption spectra, probably owing to the lower lattice energy and weaker chemical bonds of Sn(OH)4. The Sn vacancies promoted the exposure of active CoFe sites, resulting in an amorphous surface layer, modulated the conductivity, and thus enhanced the OER performance. Argon plasma can ensure preferential Sn vacancies on the surface of SnCoFe perovskite hydroxide, which exhibits a much higher current density and a lower overpotential for the oxygen evolution reaction.