Urban overheating is an increasing threat to people, infrastructure, and the environment. Common mitigation strategies, such as green infrastructure, face space limitations in current car-centric cities. In 2020, the City of Phoenix, Arizona, piloted a “cool pavement” program using a solar reflective pavement (RP) seal on 58 km of residential streets. Comprehensive micrometeorological observations were used to evaluate the cooling potential of the RP based on three heat exposure metrics––surface, air, and mean radiant temperatures––across three residential RP-treated and untreated neighborhoods. In addition, the solar reflectivity of RP was observed over seven months across eight residential neighborhoods. Results are synthesized with the literature to provide context-based RP implementation guidelines to mitigate urban overheating where common strategies cannot be applied. The three most important contextual factors to consider for effective RP implementation include urban location, background climate type, and heat metric of interest.