Titanium dioxide is a technologically interesting material in many applicative fields that, however, exhibits critical aspects in terms of phase purity and synthesis/growth conditions.The presented work deals with the deposition, in vacuum, of single-phase rutile and anatase titania films by excimer laser ablation (λ = 248 nm) of anatase and rutile targets. Post-deposition thermal treatment at 450 °C in air was applied to drive the crystalline evolution of the as-deposited films, limit oxygen desorption and avoid changes in the polymorph phase.Unlike the typical use of oxygen as a background gas and Ti target in pulsed laser deposition of TiO2, our setting vacuum background atmosphere not only allows to relate the final phase of the film directly to the target phase but also to rule out phase transitions and mixed-phase, by the interplay between post-growth temperature and limited oxygen desorption. Herein, we study and …