A novel carbon fiber aerogel was prepared by one-step direct pyrolysis method using natural cotton as a precursor, the electrolysis-ozone technology using CFA cathode (E-O3-CFA) was established. The composition and structure of CFA were analysised 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. The results showed that 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) of electrolysis-ozone technology for TOC removal was furtherly reduced by using CFA cathode. Therefore, the E-O3-CFA technology was a better strategy for the treatment of organic micro-pollutants from aqueous.