Compared with the rapid deactivation of the Pd/AC catalyst, an eco-friendly Pd-[DBU][Cl]/AC ([DBU][Cl], 1,8-diazabicyclo[^5.4.0]undec-7-ene hydrochloride) catalyst with enhanced stability was synthesized and applied in the hydrochlorination of acetylene. The Pd-20[DBU][Cl]/AC catalyst exhibits 96.7% acetylene conversion and 98.9% selectivity of vinyl chloride within the 24 h evaluation under the conditions of T = 180 °C, GHSV(C₂H₂) = 360 h^–1 and V(HCl)/V(C₂H₂) = 1.2. The enhanced stability of the Pd-[DBU][Cl]/AC catalyst is attributed to the prevention of the reduction of Pd(II) to Pd(0), the inhibition of the formation of coke deposition on the catalyst surface, and the reduction of the loss of Pd species during the reaction. TPD characterization and DFT theoretical simulations confirmed that the PdCl₂-[DBU][Cl] complex has stronger adsorption of HCl and weaker adsorption of C₂H₂ and C₂H₃Cl compared to PdCl₂. Furthermore, the catalytic mechanism of acetylene hydrochlorination over the PdCl₂ and PdCl₂-[DBU][Cl] site was put forward based on theoretical simulations. The good activity and stability of Pd-20[DBU][Cl]/AC in the 60 h lifetime test indicates that it is likely to be a promising alternative to HgCl₂ catalysts.