In this study we investigate the molecular mechanism of formation of titanicone films on anatase TiO2, rutile TiO2 and Al2O3 surfaces using TiCl4 or Ti(DMA)4 as Ti source and EG or GL as organic components. Calculated energetics suggest a higher reactivity of Ti(DMA)4 towards the selected surfaces and the organic molecules compared to TiCl4. This is due to the stronger Ti-Cl bonds in TiCl4 compared to Ti-N bonds in Ti(DMA)4. We also found that the choice of surface and inorganic precursors can influence the behavior of organic molecules by allowing or preventing undesirable double reactions. Based on the calculated energetics we propose that a low temperature rutile TiO2/TiCl4-EG process and rutile TiO2/TiCl4-GL process can lead to films with high growth per cycle.