Abstract: A non-mercuric homogenous system for hydro-chlorination of acetylene，which comprised PtCl4，81-R and 1-chlorododecane was prepared. The system was characterized by using Fourier transform infrared spectroscopy and ultraviolet-visible spectroscopy. The active component was the ion-association complex [PtCl6]2-[RNH3]2+，and the reaction mechanism on this catalyst system was proposed. The performance of different applications with multiple catalyst promoters was compared through orthogonal experiments. The results showed that when the concentration of Pt+ was 0.005mol/L，the average conversion in the first 20 hours could be more than 80%，with the selectivity above 99%.