To improve extraction performance of carbon fibers (CFs) towards phthalate esters (PAEs), titanium dioxide (TiO) nanorods array was in-situ grown on the surface of CFs, then polyaniline (PANI) was used to modify it. PANI/TiO nanorods-CFs were placed into a polyetheretherketone tube for solid-phase microextraction (SPME). Combining the tube to high performance liquid chromatography (HPLC), it was evaluated and displayed good extraction performance for several PAEs.