Hydroxyl and nitrogen rich groups-containing tung-oil-based Ca/Zn (Ca-HTMA-1, Zn-HTMA-1, Ca-HTMA-2 and Zn-HTMA-2) and polyol thermal stabilizers (HTMA-1 and HTMA-2) were successfully synthesized from tung-maleic anhydride (TMA). The thermal stability tests show that CaSt(2)/Zn-HTMA-2/HTMA-2 displays the best thermal stability for poly(vinyl chloride) (PVC). The superior performance is attributed to the synergistic effect of CaSt(2), Zn-HTMA-2 and HTMA-2, which is originated from the simultaneous introduction of hydroxyl and nitrogen rich groups into the Zn-HTMA-2 and HTMA-2 structures. The nitrogen rich groups can absorb the hydrogen chloride released during the PVC degradation process, which helps to inhibit the autocatalytic effect and lead to better long term thermal stability. Besides, hydroxyl groups can form stable chelates with ZnCl2 to avoid zinc-burning during the later PVC degradation. Besides the better stabilization performance, CaSt(2)/Zn-HTMA-2/HTMA-2 also displays comparable plasticization performance for PVC compared with other stabilizers. A possible stabilizing mechanism of PVC/CaSt(2)/Zn-HTMA-2/HTMA-2 system was presented.