The effects of molybdenum trioxide on smoke suppression of PVC were studied by FTIR , XRD and smoke density measurement. It's discovered that molybdenum trioxide is an excellent smoke suppression for PVC.The results of molybdenum trioxide on smoke suppression of PVC is attributed to the changing pattern of thermal decomposition ,reducing thermal decomposition rate and increasing char residue. It has been proved that the effect of molybdenum trioxide on smoke suppression of PVC is in condensed phase.