Active and stable supported metal catalysts, with low metal loading amount and easy access if possible, are preferentially considered and synthesized. This study reports a novel synthesis strategy to prepare Mott-Schottky type nitrogen-doped carbon supported single-atom iron SA-Fe/Nx-C catalysts by ligand-coordinated metallic method together with carbon nitride as template agent and nitrogen source for selective oxidation of benzyl alcohol to benzaldehyde. The SA-Fe/Nx-C catalysts exhibited excellent catalytic performance in benzyl alcohol oxidation compared to that of Fe nanoparticle-based catalyst. The reason for high catalytic activity was attributed to the formed tetra-coordinated FeN4 structure on which electron transfer occurred from metallic Fe to N atoms in the interface of Mott-Schottky contact. Moreover, by tuning the ratio of carbon nitride in preparation of catalysts, the N content doped into carbon could be regulated, accomplishing controllable adjustment of electron transfer of metallic Fe and thus improving the selective benzyl alcohol oxidation.