Commercial activated carbon fiber (ACF) has been employed as particle electrodes to degrade aqueous m-cresol in 3-D electrode systems. To enhance the electrooxidation performance, three types of new ACF modification modes (anodic oxidation, cathodic reduction, and aqueous oxidation with concentrated HNO3) were introduced in this paper. These pretreated samples were characterized by N2 adsorption, scanning electron microscopy (SEM), cyclic voltammetry (CV), temperature-programmed desorption mass (TPD-MS), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FT-IR). It was revealed that the two new modification methods could efficiently modify the surface morphology as well as the chemical property. Eight types of surface oxygen groups (SOGs) were identified on the surface of ACF, and the types and amount of SOGs might be related to the oxidation effect of ACF on the 3-D electrodes. The effect and mechanism of these SOGs on electrooxidation performance were discussed with the aid of the frontier molecular orbital theory. It was demonstrated that the H2O2–·OH reaction mechanism was improved in the 3-D electrode system and the mechanism was elucidated.