In this study, electrospinning technology, physical activation, and carbonization processing were applied to produce lignosulfonate-based activated carbon fibers. The porous structure of the produced lignosulfonate-based activated carbon fibers primarily contained mesopores and a relatively small amount of micropores. Moreover, insufficient carbonization caused fiber damage during CO2 activation. The weight loss rate and specific surface area increased with increase in carbonization time, and products with carbonization temperatures of 700 °C were of higher quality than those with other temperatures. Moreover, the two-step carbonization process provided fibers with improved quality because of a low weight loss rate, improved processing, and high surface area. Lignosulfonate-based activated carbon fibers can be used as a highly efficient adsorption and filtration material, and further development of its applications would be valuable.