Vanadium dioxide (VO2) is widely recognized as a thermochromic material with great potential for application in smart glazing for energy-efficient buildings. The monoclinic (M1) VO2 phase undergoes a first-order reversible phase transition from the semiconductor to the rutile metallic state. In this study, an M1 VO2 porous film was synthesized via a polymer-assisted sol-gel route. Processing parameters, such as drying and reduction temperatures, were varied to evaluate their influence on the thermochromic behavior of VO2 and to determine the necessary trade-off between a significant thermochromic effect and high luminous transmittance. Film–silica glass–film systems with luminous transmittance close to 80% and IR solar modulation ability as large as 20% were prepared. By tracking the optical constants of the films during the thermochromic process, the changes produced at the microscopic level in the material could be correlated with its macroscopic behavior when used as an energy-saving material.