Evaporative emissions, a major cause of air pollution, are primarily produced by automobiles and can be recovered using adsorbents. This study investigated the effect of the textural properties of polyimide (PI)-based activated carbon fibers (PIACFs) on the adsorption and desorption performance of n-butane, which are a type of evaporative emissions. PI-ACFs were prepared by varying the activation time while maintaining the identical crosslinking and carbonization conditions. The surface morphology and microstructural properties of the ACFs were examined using a field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD), respectively. The textural properties of ACF (specific surface area, pore volume, and pore size distribution) were analyzed using N2/ 77 K adsorption and desorption isotherm curves. The n-butane adsorption and desorption performance were evaluated according to modified ASTM D5228. From the results, the specific surface area and total pore volume of ACFs were determined to be 680–1480 m2/ g and 0.28–1.37 cm3/ g, respectively. Butane activity (BA) of the ACFs increased from 14.1% to 37.1% as the activation time increased, and especially it was found to have highly correlated with pore volume in the 1.5–4.0 nm range.