This study, based on the ZnO/MgO–S composite vulcanization system, systematically investigated the effects of five accelerators, including sulfenamides (CZ), thiazoles (DM), thiurams (TMTD, TMTM), and tertiary amines (ACT-55), on the properties of chloroprene rubber/cis-polybutadiene rubber (CR/BR) blends. The results showed that TMTD and TMTM significantly improved the vulcanization efficiency of the blends, and the vulcanizates obtained from these systems exhibited the highest degree of vulcanization, tensile strength (reaching 18.8 MPa), abrasion resistance, and optimal low-temperature resistance (with a low-temperature brittle temperature of -44 ℃), but the retention of tensile strength after thermo-oxidative aging was poor. The blends from the CZ system exhibited the highest elongation at break, while the blends from the DM system showed the best retention of tensile strength after thermo-oxidative aging. The tertiary amine ACT-55 had the shortest scorch time and the worst tensile properties at room temperature.