Polymeric carbon nitride (PCN) shows great potential applications in the areas of sustainable energy (photocatalysis and photoelectric conversion, as well as other important catalytic reactions), biosensing, biomedicine, devices, and more, but efficient phosphorescence is very scarce because of the lack of an effective synthetic method and an unsettled phosphorescent mechanism. Herein, we report a strategy to promote efficient phosphorescence to activate triplet exciton release by introduction of S and N elements. PCN could be synthesized by thiourea or urea (named S,N-PCN and N-PCN, respectively) at a relatively low reaction temperature (260 °C). S,N-PCN exhibits phosphorescence quantum yield (4.15%) higher than that (0.41%) for N-PCN. The introduction of C=S and C≡N groups in S,N-PCN networks could boost the intersystem crossing (ISC), leading to small singlet–triplet energy (ΔEST) up to more triplet exciton generation. Considering the excellent optical stability of PCN, a preliminary application of visible-light-excited PCN in advanced anticounterfeiting is proposed.