This work provides a mechanistic insight into the effects of different type of N-doped carbon-supported catalysts on the synthesis of VAc by the acetylene method. The introduction of N-doping can enhance the adsorption of acetylene and acetic acid molecules onto the catalyst supports. The N6–3 surface which with three pyridinic-N shows the most adsorption stability for both acetylene and acetic acid molecules, and facilitates the synthesis of VAc efficiently. While the N6 surface which with the pyridinic-N is obstructive to the VAc formation. Display omitted •The N-doping enhances the adsorption of acetylene and acetic acid molecules.•The activation barrier could be effectively lowered by a concerted TS1.•The N6–3 surface facilitates the VAc synthesis by acetylene method efficiently.