The invention provides a mercury-free catalyst for use in production of chloroethylene by a calcium carbide method. A supported mercury-free catalyst of which the metal bismuth simple substance is used as an active ingredient is prepared from bismuth trichloride serving as a raw material and active carbon serving as a carrier by the reduction of hydrogen; and the novel mercury-free catalyst with high activity and stability can be obtained by adding an aid. The mercury-free catalyst has the advantages of safety, no toxicity, environmental protection, low cost and the like, has the high activity and selectivity in a reaction for forming the chloroethylene by the hydrochlorination of acetylene, and can be used as an excellent substitute of a mercury-containing catalyst.