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• Nitrogen and phosphorus codoped carbon-based catalyst was successfully prepared. • Catalysts with NP-C600 gave excellent activity and stability for acetylene hydrochlorination. • The conversion of C 2 H 2 over NP-C600 is almost identical to that over Au/C. • Phosphorus atoms bonded with nitrogen in a pyridine structure are the active sites for the best-performing NP-C600 catalyst. Catalyzed acetylene hydrochlorination for vinyl chloride monomer (VCM) production is of great industrial importance, as VCM is the precursor for polyvinyl chloride. Carbon-based materials have recently been proposed as environmentally friendly and cost-efficient substitutes for highly toxic mercuric chloride catalyst, which is currently used for VCM manufacture. However, their practical application has been limited because of their relatively low reactivity, due to the lack of efficient active sites. Structural engineering of carbon-based materials has been proved a powerful strategy for tuning their physical and chemical properties, which are directly related to their catalytic properties. Here we present a novel and highly active nitrogen- and phosphorus-codoped carbon-based catalyst prepared using 1-ethylsulfonate-3-methylimidazolium dihydrogen phosphate [ESO 3 HMim+H 2 PO 4 −] as a phosphorus source and 1-ethyl-3-methylimidazolium dicyanamide [EMim]+N(CN) 2 −] as a nitrogen source, which has shown unexpectedly high acetylene hydrochlorination activity with space-time yield comparable to that of some well-developed Au-based catalysts. Experimental observations in combination with density functional theory calculations demonstrated that phosphorus atoms bonded with nitrogen in the pyridine structure are the active sites for the best-performing NP-C600 catalyst. This work provides a promising method of structure tuning of carbon-based metal-free materials to effectively optimize their catalytic mechanism and applications. [ABSTRACT FROM AUTHOR]