Polyimides (PIs) are known to have the high mechanical and thermal stability, but they have limited application for gas separation due to their low permeability. To overcome the low permeability of PIs, we developed PDMS-containing PI copolymers with different PDMS compositions as highly permeable polymer membranes. The piperazinium group was further introduced on the side chains of the PDMS-PIs both as crosslinkers and CO2-solubilizing groups. The preparation and properties of the corresponding polymer membranes for CO2 separation will be discussed.