The effect of over-heating in urban areas, called the urban heat island effect (UHI effect), is responsible for greater energy consumption for cooling buildings. Several reflective near-infrared (NIR) coatings, called cool coatings have proved to be effective for contrasting the UHI effect. The thermal and appearance properties of cool coatings depend on the color and they often have been studied only at the initial state, without undergoing atmospheric degradation and soiling. In this work, the thermal, visual and durability behaviors of red and brown polyester-based organic coatings for roof applications were studied. All samples were subjected to accelerated degradation cycles composed of UV-B and salt spray chamber exposure. The sample degradation was assessed by infrared spectroscopy, gloss and colorimetric analyses. Moreover, the thermal behavior was studied by means of a simplified experimental setup. Finally, a soiling and weathering test was conducted to simulate the soiling of three years’ external exposure. Despite the phenomena of chemical degradation and a decrease in aesthetic properties, the samples maintain their thermal performance, which is not even influenced by dirt products. In addition, NIR pigments significantly improve the thermal behavior of brown coatings.