Heterogeneous catalysts of inexpensive and reusable transition-metal are attractive alternatives to homogeneous catalysts; the relatively low activity of transition-metal nanoparticles has become the main hurdle for their practical applications. Here, the de novo design of a Mott-Schottky-type heterogeneous catalyst is reported to boost the activity of a transition-metal nanocatalyst through electron transfer at the metal/nitrogen-doped carbon interface. The Mott-Schottky catalyst of nitrogen-rich carbon-coated cobalt nanoparticles (Co@NC) was prepared through direct polycondensation of simple organic molecules and inorganic metal salts in the presence of g-C3N4 powder. The Co@NC with controllable nitrogen content and thus tunable Fermi energy and catalytic activity exhibited a high turnover frequency (TOF) value (8.12 mol methyl benzoate mol(-1) Co h(-1)) for the direct, base-free, aerobic oxidation of benzyl alcohols to methyl benzoate; this TOF is 30-fold higher than those of the state-of-the-art transition metal-based nanocatalysts reported in the literature. The presented efficient Mott-Schottky catalyst can trigger the synthesis of a series of alkyl esters and even diesters in high yields.