Production of vinyl chloride monomer (VCM) via acetylene hydrochlorination reaction (AHR) is consuming huge amount of mercury catalyst that is highly toxic. A cheap, nontoxic, and effective alternate is urgently required. Here, we designed an AuI catalyst for AHR with the excellent catalytic performance. The designed 0.1 AuI(wt %)/AC2 catalyst shows the comparable catalytic efficiency to the commercial mercury catalyst, which is applicable for industrial production of VCM. Theoretical calculations determine the activation mechanism of C2H2 by AuI, and highlight the high stability of AuI.