The study of a novel catalyst containing LiCl and SnCl2 (LiSn/AC) for acetylene hydrochlorination has been reported in this paper. Furthermore, the performance of both high activity (98.3%) and selectivity (>98.0%) are achieved by LiSn/AC catalysts under the reaction temperature of 200 °C and C2H2 hourly space velocity of 30 h−1. The structural characteristics of the Sn based catalysts were deeply researched via BET, XRD, TEM, TPR, C2H2-TPD, XPS and TG techniques. According to these characteristic results, we proposed that the presence of Sn2+ exhibited better activity and stability than that of Sn4+ in Sn based catalysts. Additionally, LiCl additives not only can restrain the oxidation of Sn2+ and the loss of Sn4+ in fresh Sn based catalysts but also make the Snδ+ (δ = 2,4) species dispersed well on the surface of support. Therefore, the adsorption capacity of C2H2 and HCl was enhanced in LiSn/AC, which exhibited the better catalytic performance than that of Sn based catalyst.