The usage of building energy accounts for 30–40% of total energy consumption in developed countries, exceeding the amount for industry or transportation. Around 50% energy for building services is contributed by heating, ventilation, and air-conditioning (HVAC) systems. More importantly, both building and HVAC energy consumptions are predicted to increase in the next two decades. Windows are considered as the least energy-efficient components of buildings. Therefore, smart windows are becoming increasingly important as they are capable of reducing HVAC energy usage by tuning the transmitted sunlight in a smart and favoured way: blocking solar irradiation on hot days, while letting it pass through on cold days. Compared with other type of smart windows, thermochromic windows have the unique advantages of cost-effectiveness, rational stimulus, and passive response. This book covers fabrication of vanadium dioxide–based smart windows, discusses various strategies to enhance their performance, and shares perspectives from the top scientists in this particular field.