The study of thermal behaviour of Ti(dpm)2(OPri)2 used as a source compound to obtain TiO2 films was carried out. Data on vapour composition, thermal stability and decomposition products of the compound in vacuo were obtained. The scheme of thermal decomposition of vapour on hot surface is suggested. Photocatalytic TiO2 films on glass and quartz substrates were obtained by chemical vapour deposition in a standard vacuum apparatus at 1.2–2.0×10−4mbar. The substrate temperature was stabilised at 450–600°C. The growth rate varied from 1–3nm/min to 20–30mn/min.