Global warming is a worldwide issue, mainly caused by excessive emission of carbon dioxide (CO2), thus, demands the development of robust and flexible sorbents with consider CO2 capturing capacity. Herein, we report an easy and facile two-step fabrication of hierarchically structured and highly porous polystyrene (PS)/polyurethane (PU) electrospun nanofiber membrane impregnated with various amines for post-combustion CO2 capture. Synthesized porous nanofiber membranes have highly flexible and strong mechanical characteristics. The comparative analysis of porous membranes functionalized with three functional amines shows that low molecular weight polyethyleneimine (PEIL) impregnated porous nanofiber membranes offer relatively higher CO2 adsorption (1.64 mmol/g) at 40 degrees C. In addition, optimized samples exhibit excellent regenerability, ( >= 90% of their original value) even after 19 adsorption-desorption cycles showing a stable and durable CO2 capture performance. This work paves the way for developing electrospun nanofiber membranes capable of efficient CO2 adsorption.