Chromium borides are promising candidates for several structural applications including protective coatings for materials exposed to corrosive and abrasive environments. In this paper the pulsed laser deposition of chromium diboride-rich thin films has been carried out in vacuum by using a frequency doubled Nd:glass laser with a pulse duration of 250 fs. The films have been deposited at different substrate temperatures and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy. Lastly, the film’s hardness has been studied by Vickers indentation technique. The results indicate that only the films deposited at a substrate temperature of 500 °C are crystalline and formed by chromium diboride, together with a certain amount of boron and chromium, which suggests that, as main mechanism, a process taking place on the surface from atoms and ions from the gas phase. This hypothesis has been confirmed by the study of the plasma produced by the ablation process.