Cool materials, with their high reflectivity, can significantly reduce the heat absorbed by buildings in summer and thus reduce energy consumption. The amount of solar radiation received by building surfaces varies with their orientation, so the effectiveness of cool materials on different building surfaces may vary. This study investigated the effects of using cool materials on scaled-down building models and full-scale real buildings through a combination of experiments and simulations, considering factors including building surfaces of different orientations, material properties, and weather conditions. Both experimental measurements and simulation studies showed that applying cool materials on roofs has the best cooling effect, reducing indoor temperatures by 0.93 °C in full-scale models. The south and west façades also showed good cooling effects when using cool materials. The north façade has the least cooling effect when using cool materials. Compared to exposed cement boards and regular materials, cool materials showed significantly better cooling effects, similar to those of 2 cm thick XPS insulation boards. Overall, buildings with poorer thermal insulation performance benefit more from the cooling effect of cool materials in summer. Additionally, the cooling effect of cool materials is ineffective on cloudy and rainy days. We found that the cooling effect of cool materials was significantly reduced when the solar radiation was less than 400 W/m2. The findings of this study provide guidance for the use of cool materials in energy retrofitting of existing buildings and the construction of low-carbon cities. •The combined experimental and simulation approach was employed.•The thermal insulation properties of four building surface materials were compared.•The cooling effect of using cool materials on different oriented building surfaces was analyzed.•Using cool materials on roofs can lower indoor temperatures by 0.93 °C for real buildings.•The effect of cool materials is significantly reduced when solar radiation is less than 400 W/m2.