The global energy system transforming from fossil fuels to renewable green energy through the adaption of innovative and dynamic green technologies. Energy‐saving buildings (ESBs) are attracting extensive attention as intelligent architectures capable of significantly reducing the energy consumption for heating, air‐conditioning, and lighting. They provide comfortable working and living environment by regulating and harnessing solar energy. Smart photovoltaic windows (SPWs) offer a promising platform for designing ESBs due to their unique feature. They can modulate solar energy based on dynamic color switching behavior under external stimuli and generate electrical power by harvesting solar energy. In this review, the‐state‐of‐art of strategies and technologies are summarized putting SPWs toward high‐efficiency ESBs. The SPWs are systematically categorized according to the working principle and functional component. For each type of SPWs, material and architecture engineering are focused on to optimize operation mode, optical modulation capability, photovoltaic performance and durability for giving ESBs flexible manipulation, extraordinary energy‐saving effect, and high electricity power. In addition, the challenges and opportunities in this cutting‐edge research area are discussed, with the aim of promoting the development of advanced multifunctional SPWs and their application in high efficiency ESBs.
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