A sulfidization roasting-flotation process was usually viewed to be effective in treating the refractory oxide ore. In this paper, pyrite was proposed to be applied as a potential vulcanizing reagent to transform PbO or its surface to PbS based on feasibilities of technology and economy. The evolution process, phase and characteristics of crystal growth were investigated by TG, XRD and SEM-EDS, respectively, to interpret the interaction mechanism of lead oxide and pyrite at high temperature. It was found that the decomposition process of pyrite under argon atmosphere was a slow process of sulfur released from FeS2 to FexS, which made the process easier to be controlled. When PbO was introduced into the system, the initial solid-solid (PbO-FeS2) reaction and prevailing solid-gas (PbO-S2(g)) reaction occurred at about 500 °C and 700 °C, respectively. Combined with the SEM-EDS analyses results, the optimal temperature for the sulfidization of PbO should be in the range of 700-750 °C