BackgroundIt is not uncommon to study the preparation of porous carbon materials for CO2 adsorption, but it is still a challenge to simultaneously achieve the good mechanical strength, porous structure, and efficient adsorption performance of porous carbon fibers. MethodsPorous carbon fibers with desirable morphology and selective CO2 adsorption were prepared using an activation-free method. The fibers were prepared through melt spinning of phenolic resin modified with polyvinyl butyral (PVB) and urea, followed by curing treatment, and then the pore structures were adjusted by controlling the carbonization temperature. Significant findingsThe porous carbon fibers prepared by carbonization at 900 °C not only had excellent CO2 adsorption (3.48 mmol/g) but also possessed desirable tensile strength (132 MPa). Those carbonized at 700 °C showcased CO2/N2 selectivity of 57 (Ideal adsorption solution theory (IAST), CO2: N2 =15:85), and tensile strength of 148 MPa, much higher than most fibers using other methods. The study revealed that the adsorption of CO2 was mainly performed by nitrogen-containing groups and physical function through pores ranging from 0.3 nm to 0.8 nm, and the micropores between 0.3 nm and 0.6 nm were conducive to the selective adsorption of CO2/N2.