Laser-induced TiCl4 decomposition at vapour pressure was performed and comparative study of the composition and structure of thermally (at 10.6 μm) and photolytically (at 248 nm) deposited Ti-based films is presented. Emphasis was given to the less explored titanium deposition process by CO2 laser pyrolysis of TiCl4. The detailed structure of films deposited on quartz substrates was examined by scanning electron microscopy and X-ray photoelectron spectroscopy. The influence of the incident laser energy on the chemical content of the films as well as on the film growth rate was demonstrated. The results indicate that in the thermal IR decomposition of TiCl4 a multilayer structure is formed with unsaturated TiSix at the interface and oxidized phases at the surface. The photolytic process leads to films with increased purity and a specific growth morphology.