An oriented titania (brookite) film containing neither anatase nor rutile was synthesized by a new modified sol–gel method. The precursor was TiCl4 with cellulose and oxalic acid as complexing agent. The XRD results show oriented pure brookite titania thin film. The SEM micrograph shows square particles on the crack free continuous film. A diffusion of sodium from the substrate was detected by XPS. It was found that the nature of complexation, the concentration of the precursors, the polymer additive, solution media (low pH, solvent-EG) and the substrate were significant of the oriented brookite TiO2 films obtained.