Graphitic carbon nitride (g-CN) is a transition metal free semiconductor that mediates a variety of photocatalytic reactions. Although photoinduced electron transfer is often postulated in the mechanism, proton-coupled electron transfer (PCET) is more favorable pathway for substrates possessing X‒H bonds. Upon excitation of an (sp2)N-rich structure of g-CN with visible light, it behaves as a photobase – undergoes reductive quenching accompanied by abstraction of a proton from a substrate. The results of modelling allowed us to identify active sites for PCET – the ‘triangular pockets’ on the edge facets of g-CN. We employ excited state PCET  from the substrate to g-CN to cleave selectively endo-(sp3)C‒H bond in oxazolidine-2-ones followed by trapping the radical with O2. This reaction affords 1,3-oxazolidine-2,4-diones. Measurement of apparent pKa value and modeling suggest that g-CN excited state can cleave X-H bonds that are characterized by bond dissociation free energy (BDFE) ~100 kcal mol-1.