Troilite is a sulfide that occurs commonly in meteorites. In the laboratory, it can be synthesized by gas-solid reaction of metallic Fe and H2S-H2 gas mixtures. In this research, the arc-discharge method was used to synthesize troilite. The resulting spherules are up to 2–3 mm in diameter and composed of troilite, pyrrhotite and metallic Fe. Nanometer-sized hollow carbon fibres and balls occur on the surface of the spherules. The features and coexisting relationships of the constituents of the spherules were studied by X-ray diffraction (XRD), energy-dispersive X-ray spectrometry (EDS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and the phenomenon of transformation of pyrite (FeS2) into pyrrhotite (Fe1−xS), troilite (FeS) and metallic Fe under arc-discharge reducing conditions were examined.