Activated carbon-supported HgCl2 catalyst has been used widely in acetylene hydrochlorination in the chlor-alkali chemical industry. However, HgCl2 is an extremely toxic pollutant. It is not only harmful to human health but also pollutes the environment. Therefore, the design and synthesis of mercury-free and environmentally benign catalysts with high activity has become an urgent need for vinyl chloride monomer (VCM) production. This review summarizes research progress on the design and development of mercury-free catalysts for acetylene hydrochlorination. Three types of catalysts for acetylene hydrochlorination in the chlor-alkali chemical industry are discussed. These catalysts are a noble metal catalyst, non-noble metal catalyst, and non-metallic catalyst. This review serves as a guide in terms of the catalyst design, properties, and catalytic mechanism of mercury-free catalyst for the acetylene hydrochlorination of VCM. The key problems and issues are discussed, and future trends are envisioned.