The development of noble‐metal‐free heterogeneous catalysts is promising for selective oxidation of aromatic alcohols; however, the relatively low conversion of non‐noble metal catalysts under solvent‐free atmospheric conditions hinders their industrial application. Now, a holey lamellar high entropy oxide (HEO) Co0.2Ni0.2Cu0.2Mg0.2Zn0.2O material with mesoporous structure is prepared by an anchoring and merging process. The HEO has ultra‐high catalytic activity for the solvent‐free aerobic oxidation of benzyl alcohol. Up to 98 % conversion can be achieved in only 2 h, to our knowledge, the highest conversion of benzyl alcohol by oxidation to date. By regulating the catalytic reaction parameters, benzoic acid or benzaldehyde can be selectively optimized as the main product. Analytical characterizations and calculations provide a deeper insight into the catalysis mechanism, revealing abundant oxygen vacancies and holey lamellar framework contribute to the ultra‐high catalytic activity. A high‐entropy oxide material with mesoporous structure is prepared by an anchoring and merging process. It exhibits ultra‐high catalytic activity for the oxidation of benzyl alcohol. Benzoic acid or benzaldehyde can be selectively optimized as the main product by rationally regulating the catalysis parameters.