In this study, the ultrasonic irradiation in elevated pressure was used to alter the molecular weight and MWD of polystyrene. The high pressure reactor was filled with 0.5w/v% polystyrene solution, and then it was pressurized from 500psi to 4000psi. The ultrasound was irradiated in 10 minutes at each pressure, and the extract was collected and analyzed by GPC. Molecular weight distribution was predicted by log-normal and Schulz distribution function. The average molecular weight and polydispersity of polystyrene were decreased, as the pressure applied during the ultrasonic irradiation was increase. It was able to fractionate polymer material and control polydispersity by adjusting pressure in the ultrasonic irradiation.