Polymers of intrinsic microporosity (PIMs) are novel class of porous materials with well-defined microcavities and high free volume elements. As the typical soluble PIMs, PIM-1 has received much attention in the field of gas separation, pervaporation and organic solvent nanofiltration, due to its microporosity, easy processability, high surface area and superior hydrophobicity. The PIM membrane with unique rigid and contorted macromolecular backbone structure showed excellent performance in gas and liquid separation, especially high CO 2 permeance and excellent CO 2 /N 2 and CO 2 /CH 4 separation factors. In general, the PIM membranes with unique characteristics will be the most promising candidates for industrial separation.