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Dehydrochlorination of 1,2-dichloroethane (1,2-DCE) is an important oil-based way for the industrial production of vinyl chloride monomer (VCM), but has proved to be plagued by a high operating temperature and low efficiency. Therefore, environmentally friendly and metal-free catalysts are in high demand for green chemical processes. In view of the stronger electronegativity of borazine (B 3 N 3 ) and convenience of constructing a two-dimensional structure because of the coplanarity of B 3 N 3 , the acetenyl group, and the benzene ring, herein, we report a novel controllable B 3 N 3 doped activated carbon (B,N-ACs) synthesized using B 3 N 3 -containing arylacetylene resin for dehydrochlorination of 1,2-DCE. The result is activated carbon loaded with B 3 N 3 -doped carbon nanosheets on the surface due to the B 3 N 3 -containing arylacetylene resin grown on the surface of activated carbons. The B,N-ACs deliver excellent catalytic performance, with a 1,2-DCE conversion of ∼92.0% and VCM selectivity over 99.9% at 250 °C, significantly higher than that of the current catalysts in the industry. The results further verified that pyridinic-N and the internal B 3 N 3 play significant roles in this catalysis. The new green, metal-free B,N-ACs with excellent catalytic efficiency make it a promising catalyst for dehydrochlorination of 1,2-DCE to produce VCM., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)