VO2-based thin films can effectively control IR radiation and luminous transmittance at the same time; hence they find applications in smart windows, by improving the thermal performance of conventional glass ones, leading to reduced energy consumption in buildings and minimization of CO2 emissions. This study deals with the nanostructural properties of VO2 thin films, grown by Pulsed Laser Deposition (PLD) with variable thickness, as determined by electron microscopy imaging (TEM/HRTEM), spectroscopy (EELS) and post-experimental image processing.