To produce open and skinless polymer foams by using carbon dioxide (CO₂) foaming technology is a puzzle. In this work, CO₂ foaming technology and breath figures method were combined to prepare open and skinless polymer foams. The cell size in the range of 8～32 μm in core zone of the foams could be adjusted by changing foaming temperature. On the other hand, porous structures on skin layer of foams were obtained by breath figures method. Moreover, by simply changing the volume ratio of chloroform and methanol, the porous size on skin layer could be altered from 2 μm to 6 μm.