Pyrite is a sulfide mineral and is widely distributed in nature. Pyrite may transform into pyrrhotite when heated at high temperatures. In order to support processing engineering techniques and industrial applications of pyrite and pyrrhotite, it is necessary to investigate synthetic pyrrhotite, which is formed by heating pyrite in air, based on existing research. In this work, the mineralogical characteristics and stability conditions of synthetic pyrrhotite formed by heating pyrite at elevated temperatures were studied. The possible formation pathway was verified using a solid-phase reaction. X-ray-diffraction results revealed that synthetic pyrrhotite differs from natural pyrrhotite in the paragenetic association of minerals. Natural pyrrhotite and magnetite coexist in the natural pyrrhotite sample. Synthetic pyrrhotite formed by heating pyrite at 700℃ for 1 h has the paragenetic association with hematite and a small amount of pyrite and magnetite. All pyrrhotite samples were monoclinic pyrrhotite-4C (Fe7S8) and exhibit minimal differences in terms of lattice parameters. Synthetic pyrrhotite-4C was stable under 0.5–2 h of heating at 700℃ in air. It had the highest relative content by heating for 1 h. It was eventually transformed into hematite with heating periods exceeding 3 h, as was the case for pyrite and magnetite. In air, synthetic pyrrhotite-4C is mainly formed via two pathways: (1) pyrite → pyrrhotite-4C and (2) pyrite → magnetite → pyrrhotite-4C. Pathway (1) is more favorable than pathway (2). This transformation cannot be achieved by the reaction between hematite and sulfur.