Air quality is strongly affected by greenhouse gas emissions contributing to climate change. Air pollution caused by the release of gases into the atmosphere, leading to global warming, has become a serious problem, especially in industrialized countries. Among these gases, CO2 is one of the most important components with high emissions originating from power plants, automobiles, and industries and it causes serious environmental problems. In recent years, polymeric nanofibers with improved strength and high surface area have been developed by electrospinning technique, which is an easy and inexpensive method. Electrospun polymeric nanofibers are promising materials for CO2 capture because of their unique properties. This chapter first focuses on the electrospinning technique and the importance of the manufacturing parameters on nanofiber structure. This is followed by the preparation of electrospun nanofibers from different polymers and their use in CO2 capture. Finally, with the integration of nanoparticles into a polymer matrix, the preparation of composite polymeric nanofibers and their use and importance in CO2 capture are also discussed.