The formation of porous glass ceramic via core/shell-structured poly(methyl methacrylate)(PMMA)/powder glass was investigated. Core/shell structures were prepared via ultrasonic irradiation in high-pressure liquid carbon dioxide (CO2) using PMMA microspheres as the core material and glass powder as the shell material. The mean particles sizes of PMMA template microspheres and glass powder were 9.8 mu m and 0.9 mu m, respectively. After removal of the PMMA template by calcination in air, porous glass was obtained. The products were characterized by scanning electronic microscopy (SEM) and thermogravimetric-differential thermal analysis (TG-DTA). The average pore diameter of porous glass was 4.3 mu m. Compared with porous glass prepared by the other method, the porous glass prepared by ultrasonic irradiation of liquid CO2 was achieved the narrow pore size distribution (CV = 35%) and the higher porosity (89%). The pores are not isolated and connected each other. Furthermore, the effects of experimental conditions, such as coating method, crosslink density of the template PMMA microspheres, ultrasonic intensity and calcination temperature, on the product morphology were investigated. The higher ultrasound intensity achieved the uniform coating of PMMA templates with powder glass. The calcination temperature and crosslinked density of PMMA template microspheres affect the pore structure. (C) 2011 Elsevier B.V. All rights reserved.