Rutile phase TiO 2 thin films have been synthesized using chemical spray pyrolysis of titanyl acetylacetonate TiAcAc in ethanol at 500°C. The first part of the paper focuses on the thermal decomposition behavior of the precursor by simultaneous thermogravimetry and differential thermal analysis (TG/DTA) coupled with differential scanning calorimetry (DSC). The second part of the paper focuses on the evolution of TiO 2 thin films and their structural transformation with substrate temperature. XRD revealed amorphous TiO 2 thin film at low substrate temperatures (<350°C) and on high substrate temperatures anatase (3.84g/cm 3 ) or rutile (4.25g/cm 3 ) crystalline structure was obtained. The lattice constant, grain size, microstrain and the dislocation density of the film were obtained from the peak width. FTIR spectra of both anatase and rutile TiO 2 revealed stretching vibration of the Ti–O bond for tetrahedral and octahedral surroundings of the titanium atom. Scanning electron micrograph showed the compactness of the rutile film.