Highly oriented thin films of alpha-alumina have been grown by pulsed laser deposition on Si(lll). The influence of the substrate temperature on the film growth was studied by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (MID). Ablation at temperatures between room temperature and 850 degrees C gave rise to incorporated crystalline aluminium (Al), while the stoichiometric and highly oriented alpha-Al2O3 films were obtained only at 850 degrees C. The XRD rocking curve measurements of the ablated films showed the full-width-at-half-maximum (FWHM) Of 0.2 degrees. Further annealing at 1000 degrees C in air for 26 h slightly improved out-of-plane orientation.