Structural changes for mechanically activated pyrite, sphalerite, galena and molybdenite with or without the exposure to ambient air, were systematically investigated using X-ray diffraction analysis(XRD), particle size analysis, gravimetrical method, X-ray photo-electron spectroscopy(XPS) and scanning electron microscopy(SEM), respectively. Based on the above structural changes for mechanically activated sulfide ores and related reports by other researchers, several qualitative rules of the mechanisms and the effects of mechanical activation for sulfide ores are obtained. For brittle sulfide ores with thermal instability, and incomplete cleavage plane or extremely incomplete cleavage plane, the mechanism of mechanical activation is that a great amount of surface reactive sites are formed during their mechanical activation. The effects of mechanical activation are apparent. For brittle sulfide ores with thermal instability, and complete cleavage plane, the mechanism of mechanical activation is that a great amount of surface reactive sites are formed, and lattice deformation happens during their mechanical activation. The effects of mechanical activation are apparent. For brittle sulfide ores with excellent thermal stability, and complete cleavage plane, the mechanism of mechanical activation is that lattice deformation happens during their mechanical activation. The effects of mechanical activation are apparent. For sulfide ores with high toughness, good thermal stability and very excellent complete cleavage plane, the mechanism of mechanical activation is that lattice deformation happens during their mechanical activation, but the lattice deformation ratio is very small. The effects of mechanical activation are worst.