Zinc-ethanol metal alkoxide was primarily synthesized as an intermediate material toward zinc-mannitol alkoxide (Zn-Man), which was further prepared through the alcohol exchange reaction with the zinc-ethanol alkoxide by mannitol. The synergistic effects of Zn-Man with several commonly used thermal additives such as calcium stearate (CaSt(2)), zinc stearate (ZnSt(2)), CaSt(2)/ZnSt(2) and stearoyl benzoyl methane (beta-diketone) on poly(vinyl chloride) (PVC) thermal stability were investigated from conductivity measurement, thermal aging testing and Ultraviolet-visible (UV-vis) spectroscopy. The thermal stability tests showed that Zn-Man distinctly prolonged the long-term thermal stability of rigid PVC. If used with CaSt(2)/ZnSt(2) or beta-diketone, the thermal stability time (T-s) increased to 165.2 and 164.7 min, respectively, from the initial 101.5 min of PVC stabilized with pure Zn-Man, but excess dosage of CaSt(2)/ZnSt(2) or beta-diketone deteriorated the long-term thermal stability. The initial coloring was excellently improved when Zn-Man combined with ZnSt(2), CaSt(2)/ZnSt(2) or beta-diketone; while the synergistic effect between Zn-Man and CaSt(2) was not significant. Moreover, testing results demonstrated that the optimal mass ratio of 3/1 showed better synergistic effects. The thermal stabilizing mechanism was also investigated through the combination of theoretical analysis and experimental testing.