Based on the synthesis of the major minerals in the matte-heazlewoodite and chalcocite，this paper, using varied means of detemination as X-ray powder diffraction analysis，electron probe analysis and electron spectroscopy for chemical analysis，expounds the examination of the occurrence state of Ni and Cu ions in the crystal structure of heazlewoodite. Studies show that nickel exists as Nit+and metallic atom in heazlewoodite, so that the existence of metal-metal bonds of Ni3S2 is confirmed. Copper has entered the crystal lattice of heazlewoodite in the form of Cu+ which partly replaces Ni2+. The unit cell dimensions of heazlewoodite containing copper in the solid solution are larger than those of heazlewoodite not containing copper, with the increments being。0. 0426A and c 0.0597A .Electron microprobe analysis shows that heazlewoodite contains 1.63 wt% Cu in solid solution at low temperature.