TiO2 thin films obtained by sol-gel and dipping deposition on glass fibers substrates followed by thermal treatment was used in this works. In an attempt to understand the structure and the morphology of TiO2 sol-gel thin films, analysis by X-ray diffraction (XRD) and scanning electron microscopy (SEM) are reported. Degradation of toluene under 365 nm light illumination was conducted to evaluate the photocatalytic ability of the TiO2 thin films. A special design of glass reactor allowed the UV lamp to be located in the center of the reactor. The photocatalyst reactor was then filled with TiO2 thin films/glass fibers substrates to exams the photocatalysis of toluene vapor ranged from 10 to 1,000 ppmv. Toluene depletion was sampled by gas chromatography (GC). The results showed that the photocatalytic performance of the reactor had high toluene depletion efficiency of 99.9% under 20 ppmv, and the efficiency decreased when toluene concentration were 100 and 1,000 ppmv. The improvement of the photocatalytic activity was ascribed to the fibers-based reactor provides a significantly huge surface area of the TiO2 thin films. These results will be useful and assist engineers to design photocatalyst reactors for the VOCs removal.