VO₂, which undergoes semiconducting-metallic phase transition, is a promising thermochromic material that can intelligently control the transmittance of sunlight in the near-infrared region in response to ambient temperature changes. This characteristic makes VO₂ valuable for applications to thermal switches, optical sensors, information storage devices, smart windows and uncooled focal plane detectors. In the present review, we firstly introduced the physical and chemical property and the present experimental investigations of VO₂ briefly. And then we discussed in detail on the research progress in the first-principles calculations
of the phase transition mechanism of VO₂, and indicated that a coupling of Mott transition and Peierls transition may exist in the VO₂ phase transition. After that, we discussed the application of first-principles calculations in the study of modification of VO₂ through doping of either metallic or nonmetallic elements. Moreover, we pointed out the great conflicts of calculation results from different calculation methods, and more cautious should be paid when dealing with these issues. Finally, a prediction of the developing trends of first-principles calculations in the study of VO₂ was summarized.