Titanium dioxide thin films were deposited conformally over electrospun polymethyl methacrylate (PMMA) fibers by hot filament chemical vapor deposition method. Deposition rates were observed to be very high to allow for rapid coatings. Thermal annealing of as deposited materials leads the clean decomposition of the polymeric inner layer and formation of randomly distributed anatase TiO₂ nanotubes. Nanotubular TiO₂ structure was clearly identified by SEM and that structure is ideal for good photocatalytic activity because of its high surface area per unit volume ratio. FTIR and XPS results show the formation of stoichiometric TiO₂, and the crystalline form of the final nanotubes was found to be anatase (1 0 1) after XRD analysis. High photocatalytic activity of TiO₂ nanotubes under UV irradiation was observed with an apparent rate constant of 0.74 h⁻¹ for methyl orange decomposition.