The introduction of chlorine atoms into the main chain of chloroprene rubber (CR) strengthens intermolecular interactions, restricts molecular?chain mobility, and gives this rubber strong polarity. At low temperatures, molecular motion slows, causing CR molecular chains to arrange more regularly and crystallize, which increases hardness and reduces elasticity. To improve the low?temperature resistance of CR, the green low?temperature plasticizer tributyl citrate (TBC) was introduced for modification. The effects of TBC mass fraction on the vulcanization characteristics, Mooney viscosity, mechanical properties, glass?transition temperature (T_g), and brittle temperature (T_b) of CR composites were investigated. The results show that, with increasing TBC mass fraction, the Mooney viscosity of the CR compound decreases significantly, scorch time is prolonged, and the processing performance and low?temperature resistance of the vulcanizate are significantly improved. When the TBC mass fraction is 5%, the tensile strength of CR reaches its maximum value of 12.16 MPa, resilience reaches its maximum value of 50.65%, permanent compression set decreases to its minimum value of 9.64%, elongation at break increases to 497.59%, and T_g decreases to -34.5 ℃. These results indicate that the modified CR exhibits simultaneous improvements in low?temperature resistance and mechanical properties, thereby expanding its applicability under low?temperature operating conditions.