Composites of titanium dioxide (TiO₂) immobilized on carbon fibers (CFs) were synthesized by a two-step process. Acid-treated CFs were dip-coated in a TiO₂ sol and then annealed under superheated steam ambient to form TiO₂/CF composites. The effects of titanium sol concentration and annealing temperature on the micromorphology and phase structure of the TiO₂/CF were investigated by field emission scanning electron microscopy and X-ray diffraction, respectively. The photocatalytic properties of the as-prepared TiO₂/CFs were evaluated by photocatalytic degradation of acid orange II under ultraviolet light irradiation. The TiO₂/CF composites prepared by superheated steam annealing exhibited a uniform surface morphology and high loading degree. The photocatalytic degradation of acid orange indicated that the TiO₂/CF composites exhibited excellent photocatalytic performance and reached up to 98.7% degradation rate after 2.5 h of irradiation.