Ar/O plasma irradiation is proposed for post-treatment of vanadium dioxide (VO2) films. Oxidation and surface migration were observed in the VO2 films following irradiation. This combined effect leads to an effective stoichiometry refinement and microstructure reconstruction in the interfacial area. A notable improvement in luminous transmittance and an enhancement in phase transition performance of the treated VO2 films were achieved. Compared with that of as-deposited VO2 films, the electrical phase transition amplitude of treated films increased more than two-fold. The relative improvement in luminous transmittance (380–780 nm) is 47.4% (from 25.1% to 37%) and the increase in solar transmittance is 66.9% (from 29.9% to 49.9%), which is comparable to or better than the previous work using anti-reflection (AR) coatings or doping methods. The interfacial boundary state proved to be crucial and Ar/O plasma irradiation offers an effective approach for further refinement of thermochromic VO2 films.