The thickness of vanadium dioxide (VO2) films is a crucial parameter for the study of their optical and thermal properties. In this paper we studied the effect of the film thickness on the thermal hysteresis loop during the phase transition of VO2 deposited on a sapphire substrate by pulsed laser deposition (PLD), by the application of the Infrared Thermography technique. We measure the main thermal hysteresis parameters of VO2 samples with different thicknesses in the LWIR range (8–14 μm) showing how the transition temperature during the heating and cooling cycles, and the width of the hysteresis loop, may change with thickness. We analyzed and compared the obtained results with, in situ Grazing Incidence X-Ray Diffraction (GI-XRD). A good agreement between the results obtained with the two techniques was found demonstrating the reliability of the IR Thermography as a quantitative characterization tool.The results show that the structural and IR emissivity properties of the VO2 layer exhibit a dynamic range dependent on the layer thickness due to a correlation with the crystalline grain size. This has important effects in view of a tailored energy management for the use of those materials as smart radiators or smart windows.