Deposition of TiO2 thin films are studied using a newly developed in situ mass spectrometry technique to observe gas phase reactions. Atmospheric pressure chemical vapour deposition (APCVD) reactions were carried out using titanium chloride and titanium tetraisopropoxide precursors, with ethyl acetate acting as an oxygen source in the case of the former, depositing on to float glass substrates at 300 and 600 °C. Using an atmospheric sampling mass spectrometer, the vapour phase was analysed during deposition and signals assigned to intermediate species that were measured during the formation of the thin films. The films deposited were characterised via scanning electron microscopy, X-ray photoelectron spectroscopy and thin film X-ray diffraction analysis.