In this work, a new type of solid amine sorbent was developed for low concentration CO₂ capture at ambient temperature. Polyacrylonitrile(PAN)-poly(methyl methacrylate)(PMMA) porous hollow fibers were firstly prepared by a wet-spinning process. Tetraethylenepentamine(TEPA) was then grafted onto the porous structure of the hollow fibers. The amine modified hollow fibers denoted as TEPA@PAN-PMMA were characterized by the Fourier transform infrared spectroscopy (FT-IR), thermo-gravimetric analysis(TGA), Brunauer-Emmett-Teller(BET), and scanning electron microscopy(SEM) methods. Performance of the TEPA@PAN-PMMA for CO₂ capture was evaluated by passing a 0.3% CO₂-N₂ gas mixture through the porous matrix of the hollow fibers at ambient temperature. The highest CO₂ adsorption capacity reached up to 1.50 mmol g⁻¹ for dry feed, and 3.00 mmol g⁻¹ for wet feed, respectively. Cyclic CO₂ adsorption-desorption test indicated that the TEPA@PAN-PMMA sorbents are stable and regenerable.