Hollow MnOx/TS-1 shows high activity for selective oxidation of ethylbenzene. 37% ethylbenzene conversion and 68% acetophenone selectivity are achieved. A favourable synergistic effect between MnOx and TiO4 species occurrs. Lower-nuclearity Mn species promote a yield of radical continuously for recycle. The exclusive oxidation of methylene CH bond of ethylbenzene is rationalized.