Calcium zinc monomer salts were prepared via simple one-step double decomposition reaction with the aid of DA and PR as raw materials. FTIR analysis demonstrated that calcium zinc monomer salts of DA and PR have been successfully synthesized. The synergistic effect between DA-based and PR-based calcium zinc monomer salts, the effects of addition amount of DOP and the synergistic effects between epoxidized soybean oil (ESO) and calcium/zinc stabilizers on thermal stability of PVC were analyzed by means of the Congo-red paper, torque rheometer and thermogravimetric analysis methods. The results showed that preferable synergistic stabilizing effects were observed when DA calcium/zinc salt and polymerized rosin calcium/zinc salt were used together. In addition, appropriate dosage of DOP could inhibit the thermal degradation of PVC, and ESO also have certain synergetic effect with prepared novel calcium/zinc stabilizers.