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Chloroprene rubber vulcanizates containing different types and amounts of curing systems were prepared by mechanical blending, and the effects of a new high-efficiency curing agent, ferric acetylacetonate [Fe(acac)3] on the curing mechanism, kinetic parameters and mechanical relaxation behavior of chloroprene rubber were investigated. The results showed that the Fe(acac)3 curing system had the characteristics of being able to participate in the vulcanization cycle during the vulcanization process when Fe(acac)3 of 0.10 phr (mass, similarby hereinafter)was used, chloroprene rubber could be vulcanized efficiently. Compared with the traditional metal oxide curing system, the tensile strength was higher and the equilibrium value of tensile stress relaxation of the vulcanizate was larger when Fe(acac)3 of only 0.25 phr was used. After 3 d of thermo-oxidative aging at 100 ℃, the vulcanizates still maintained a high compressive stress relaxation equilibrium value due to the characteristics that Fe(acac)3 curing system was capable of participating in the vulcanization process circularly.