This paper holds a critical review of current research activities dealing with smart architectural glazing worldwide. Hereafter, the main trends are analyzed and critically reported, with open issues, challenges, and opportunities, providing an accurate description of technological evolution of devices in time. This manuscript deals with some well-known, highly performing technologies, such as semitransparent photovoltaics and novel photoelectrochromic devices, the readiest, probably, to reach the final stage of development, to disclose the manifold advantages of multifunctional, smart glazing. The complex, overall effects of their building integration are also reported, especially regarding energy balance and indoor visual comfort in buildings.