A study of the laser ablation and deposition, on Ti6Al4V substrates, of a biological active glass (Bioglass (R) 45S5) is reported. The gaseous phase composition has been determined by laser ablation inductively coupled plasma mass spectrometry, optical imaging and emission spectroscopy. The deposited films were studied by scanning electron microscopy coupled with energy and wavelength dispersive X-ray analysis and X-ray diffraction. The adhesion of films to the substrates has been studied by scratch tests. Moreover, after exposing the coatings to a simulating body fluid solution. their bioactivity has been monitored by X-ray diffraction analysis of the hydroxylapatite growth. This procedure has been followed for different time scales up to a maximum of 24 days. The deposition mechanism seems to be related mainly to the mechanical transport of the target material in form of droplets, while the gaseous phase, having a very different composition, plays a marginal role. The overall film retains the target stoichiometry and bioactivity in a large range of experimental conditions.