The adsorption of volatile organic compounds (VOCs) on phenolic-based carbon fibers is a current research hotspot. However, research on the inner association between preoxidation, carbonization, and adsorption performance is insufficient. This work studied the electrospinning, preoxidation, and carbonization conditions of thermosetting phenolic resin and the relevant effects on the VOC adsorption performance of derived activated carbon fibers. The static and dynamic adsorption performances of benzene over four types of carbon fibers were tested, and oxygenated VOCs (OVOCs) were introduced for binary VOC competitive adsorption tests. The results indicate that a proper amount of auxiliary agent promises continuous fibers and chemically associates with resole during electrospinning and preoxidation. Moreover, a proper curing time and high carbonizing temperature endow carbon fibers with a high surface area and excellent adsorption performance. Finally, the small-sized basal planes and amorphous sp 2 clusters readily adsorb benzene with the strong π−π interaction, which essentially determines the competition performance between OVOCs and benzene.