Securing net-zero targets by employing sustainable materials for the built environment is highly desirable, and this can be achieved by retrofitting existing non-smart windows with thermoelectric (TE) glazing, providing improved thermal performance along with green electricity production. It is reported that TE glazing could produce ~4000 kWh of power per year in a cold climate with a temperature differential of ~22 °C. This feature of TE materials drives their emplacement as an alternative to existing glazing materials and could lead to the identification of optimum solutions for smart window development. However, few attempts have been made to employ TE materials in glazing. Therefore, in this brief review, we discuss, for the first time, the efforts made to employ TE in glazing, identify their drawbacks, and discuss potential solutions. Furthermore, the working principle, suitable materials, and methods for developing TE glazing are discussed. In addition, this article introduces a new research area and provides researchers with detailed instructions on how to build and optimize this system. The maximum efficiency of a thermoelectric material is determined by its thermoelectric figure of merit, which is a well-defined metric to characterize a device operating between the hot-side and cold-side temperatures. TE material’s figure of merit promises new perspectives on the conceivable future energy-positive built environment. The role of TE in tackling the energy crisis is also discussed, since it provides sustainable energy alternatives