The present work reports preparation of ordered mesoporous carbon (OMC) film supported on a graphite fiber as a new type of solid-phase microextraction (SPME) fiber for determination of benzene series from aqueous media. The strategy for the supported OMC film preparation was combined dip-coating technology with solvent evaporation-induced self-assembly (EISA) approach. A graphite fiber was immersed in an ethanol solution containing phenolic resin and Pluronic triblock copolymer. Upon solvent evaporation and subsequent pyrolysis under 700 °C, the phenolic resin and the surfactant self-assembled on the surface of the graphite fiber to form smooth OMC film. X-ray diffraction (XRD), transmission electron microscopy (TEM) and nitrogen isothermal adsorption results indicate that the resultant OMC film possesses well-ordered two dimensional hexagonal mesostructure with pore diameters of 4.5 nm and BET surfaces of 630 m(2)/g. Scanning electron microscopy (SEM) studies show the supported OMC film with thickness at 8.5 μm is continuous and defect-free. The SPME efficiency of the OMC fiber was evaluated by analysis of five benzene series (benzene, toluene, ethylbenzene, p-xylene and m-xylene) from water samples by gas chromatography-flame ionization detection (GC-FID). The analysis results indicate that the prepared OMC fiber has wide linear ranges (0.5-500 μg/L), low detection limits (0.01-0.05 μg/L) and good repeatabilities (4.0-5.8% for one fiber, 2.9-8.7% for fiber-to-fiber). Compared with commercial counterparts, the OMC fiber exhibits improved extraction efficiency for benzene series and PAHs.