In this work, VO2 (M1/R) thin films were exploited as H2 gas sensors. A flat film morphology, obtained by furnace annealing, was compared with a laser-induced nanostructured one. The combination of the environmentally friendly sol-gel approach with the ultrafast laser crystallization allows for significant reductions in energy consumption and related emissions during the fabrication of VO2 sensors. By decorating the sensors' surface with Pt nanoparticles (NPs), the sensor response was enhanced exploiting the hydrogen spillover effect. The Pt/VO2 sensors, tested at operating temperatures between 20 and 200 °C and for concentration of H2 from few ppm to 50000 ppm, offered a dual chemoresistive and optical sensing mode. Low operating temperatures of 150 °C were achieved, along with a detection limit as low as 2 ppm and a perfect baseline recovery. Both sensors guaranteed specific selectivity toward H2, without response to NO2 or humidity, and long-term stability over 500 h. The H2 sensing mechanism, for both the monoclinic and rutile VO2 phases, was investigated through in operando X-ray Diffraction and in situ X-ray Photoelectron Spectroscopy tests. The interaction was found to be based on the reversible formation of HxVO2 bronze, along with the reversible variations in the oxidation state of V.