The acid‐base microenvironment of the metal center is crucial for constructing advanced oxygen evolution reaction (OER) electrocatalysts. However, the correlation between acidic site and OER performance remains unclear for cobalt‐based catalysts. Herein, Lewis acid sites in hollow cobalt phytate micropolyhedra (M‐CoPA, M = Cu, Sr) were synthesized by a cation‐exchange strategy, and their OER performances were studied systematically. Experimentally, Lewis acid Cu2+ sites with stronger Lewis acidity exhibited superior intrinsic activity and long‐term stability in alkaline electrolytes. The spectroscopic and electrochemical studies show Lewis acid sites in hollow cobalt phytate micropolyhedra can modulate the electronic distribution of the adjacent cobalt center and further optimize the adsorption strength of oxygenated species. This study figures out the effect of Lewis acid sites on the OER kinetics and provides an effective way to develop high‐efficiency electrocatalysts for energy conversion systems.