Thin films of crystallized LaCoO3 were grown on Si substrate by Pulsed Laser Deposition at different temperatures (750°C, 850°C and 1000°C). The structural characterization of the LaCoO3 thin films was done by combining several techniques: Scanning Electron Microscopy (SEM), Atomic Force Microscope (AFM), Transmission Electron Microscopy (TEM) and Grazing Incidence X-Ray Diffraction (GIXRD). The thin films crystallized in the expected rhombohedral phase whatever the deposition temperature, with an increase of crystallite size from 70 nm at 750°C to 100 nm at 1000°C, and an average thickness of the thin films of less than 200 nm. At 850°C and 1000°C, the thin films are crack-free, and with a lower number of droplets than the film deposited at 750°C. The grains of LaCoO3 film deposited at 850°C are columnar, with a triangular termination. At 1000°C, an intermediate layer of La2Si2O7 was observed, indicating diffusion of Si into the deposited film.