A novel carbon fiber aerogel was prepared by one-step direct pyrolysis method using natural cotton as a precursor, and the electrolysis-ozone technology using CFA cathode (E-O₃-CFA) was established. The composition and structure of CFA were analyzed by SEM, BET and XPS. The removal of IBP and the main operational parameters (e.g., cathode materials、current intensity、ozone concentration and pH) were evaluated systematically. The pathway and mechanism of IBP removal were also investigated, and the energy consumption was calculated. The results showed that CFA is a porous interconnected three-dimensional network structure with developed pores, high specific surface area and abundant oxygen-containing functional groups on the surface. The removal rate of IBP by E-O₃-CFA process was 97.96% at ozone concentration of 16mg/L, current intensity of 300 mA, and without adjusting the initial pH. It was higher than the electrolysis-ozone technology with other cathode (steel cathode 83.11%、activated carbon fiber cathode 94.78%、graphite cathode 89.05%). The IBP was mainly removed by the free radical oxidation pathway by ·OH. Moreover, the specific energy consumption (SEC=2.49 kW·h/gTOC) of electrolysis-ozone technology for TOC removal was furtherly reduced by using CFA cathode.