Although moissanite has been found in various rocks, reliable primary moissanite has been reported only from kimberlites and meteorites. The Dabie Mountain moissanite reported in this paper is the first occurrence of primary moissanite hosted by serpentinite. It differs from synthetic silicon carbide in optical properties, inclusions and infrared spectrum. The biaxiality of the Dabie Mountain moissanite is thought to be the result of intracrystal deformation. In reference to the ultrahigh pressure (7–8 GPa) signature of exsolution of rod-like apatite, clinopyroxene and rutile in garnets, and magnetite lamellae in olivine reported in the Dabieshan, we inferred that the moissanite from the Dabie Mountains was probably generated at a depth of 180 km; and then subducted to a depth of 210–250 km, where the moissanite became biaxial before its exhumation.