The selective oxidations of alcohols into corresponding aldehydes or ketones are essential reactions for organic synthesis. The development of facile, green and cost-effective protocols to accomplish selective oxidation is highly attractive. Here, we present the selective oxidation of alcohols using peroxymonosulfate (PMS) oxidants with N-doped graphene-like carbon (NG) synthesized via a metal-free approach without producing a large amount of hazardous wastes. In the tested selective oxidation reaction, over 96% of benzyl alcohol (BzOH) was converted into benzaldehyde (BzH) with high selectivity under mild conditions. The synthesized NG catalyst contains abundant electrophilic oxygen species, serving as the major active sites for the generation of reactive radicals from PMS to enable the selective oxidation of BzOH in the radical pathway. Besides, non-radical oxidation of BzOH occurs via the electron transfer through the surface coordinated complex, dominantly upon the N species. Particularly, the configuration of integrated pyridinic N is possible to create active domains for BzOH oxidation with activated PMS. This work opens a new avenue to convert metal-free raw materials into effectively functionalized carbon materials, coupled with their potential applications in the selective oxidation of alcohols.