The human activities such as burning of fossil fuels, deforestation, and industrial processes, which release greenhouse gases (GHGs) such as carbon dioxide, methane, and nitrous oxide into the atmosphere, are the primary drivers of climate change. As a consequence, the average surface temperature is continuously increasing. In urban areas, this phenomenon is more pronounced, contributing to the urban heat island (UHI) effect, which directly impacts the health of vulnerable populations and the increase in energy consumption. At present, among the most common measures applied to contrast the heat island effect are cool and energy harvesting pavements. This chapter starts with a summary of UHI intensity data for various cities around the world, highlighting cool pavements as the most promising solutions. Then, for each technology, the working principles and governing equations are detailed. The objective of this chapter is to analyze the state of the art in cool pavement technologies and provide a critical assessment of each solution in terms of advantages, disadvantages, and effectiveness in mitigating the urban heat island effect. The review adopts an integrative approach by: identifying the most significant research addressing working principles, modeling, and UHI mitigation and assessing, critiquing, and synthesizing the literature to identify frameworks and future perspectives. In conclusion, reflective pavements are strong candidates for simple, effective, and low-cost UHI mitigation, while energy-harvesting pavements remain promising technologies that combine heat island mitigation with the ability to capture thermal energy. However, their widespread adoption is still limited by prohibitive initial costs.