Global CO2 emissions have increased steadily in tandem with the use of fossil fuels. A paradigm shift is needed in developing new ways by which energy is supplied and utilized, together with climate change mitigation through CO2 reduction technologies. Renewable energy, non-fossil fuels, and CO2 capture and storage (CCS) must be deployed on a massive scale. CCS technologies provide a means for reducing greenhouse gas emissions in addition to the current strategies for improving energy efficiency. Membrane processes offer a potentially viable energy-saving alternative for CO2 capture because they do not involve any phase transformation. Polymer membranes that are highly permeable to CO2 and have good selectivity should be developed for the membrane process to be viable. This perspective review summarizes recent noteworthy advances in polymeric materials having very high CO2 permeability and good CO2/N2 selectivity that vastly surpass the separation performance of conventional polymer materials.