A non-mercury catalyst for acetylene hydrochlorination comprises a carrier, a main active component and an assistant; the carrier is activated carbon; the main active component is a gold complex formed through complexing gold chloride and a ligand through a sigma-pi feedback bond; and the assistant is any one or a combination containing more of chlorides of copper, cobalt, nickel, lanthanum, cerium and caesium. The non-mercury catalyst has the advantages of low gold loading capacity, realization of high acetylene conversion rate and high vinyl chloride selectivity when used in an acetylene hydrochlorination reaction for synthesizing vinyl chloride, and good stability.