A substantial amount of interest has been focused on ABO(3)-type perovskite oxides over the past decade as oxygen electrocatalysts. Despite many studies on various compositions, the correlation between the structure of the oxygen octahedra and electrocatalytic property has been overlooked, and there accordingly have been a very limited number of attempts regarding control of atomistic structure. Utilizing epitaxial LnNiO(3) (Ln = La, Pr, Nd) thin films, here we demonstrate that simple electrochemical exchange of Fe in the surface region with several-unit-cell thickness is notably effective to boost the catalytic activity for the oxygen evolution reaction by different orders of magnitude. Furthermore, we directly establish that strong distortion of oxygen octahedra at the angstrom scale is readily induced during the Fe exchange, and that this structural perturbation permits easier charge transfer. The findings suggest that structural alteration can be an efficient approach to achieve exceptional electrocatalysis in crystalline oxides.