Generally, sulfur elimination from nickel matte was incomplete in the one-step oxidation roasting process. In this work, X-ray diffraction, scanning electron microscopy/energy-dispersive X-ray spectroscopy, and chemical analysis of the roasted products were carried out to explain this phenomenon. The results indicated that the melting of heazlewoodite was the main limiting factor. Thereafter, the oxidation mechanism of high-grade nickel matte from room temperature to 1000 °C was studied. It was found that the transformation from heazlewoodite (Ni3S2) to nickel sulfide (NiS) took place from 400 °C to 520 °C. Considering that the melting temperature of NiS was much higher than that of Ni3S2, a low-temperature roasting step was suggested to suppress the melting of heazlewoodite. Under the optimum conditions (520 °C for 120 minutes followed by 800 °C for 80 minutes), the degree of desulfurization reached 99.52 pct. These results indicated that the two-step oxidation roasting method could be a promising process for producing low-sulfur calcine from high-grade nickel matte.