Both cool roof and phase change thermal storage are promising technologies in decreasing building energy consumption. Combining these two technologies is likely to further enhance the thermal comfort of the building as well as reduce air condition loads. In this paper, the cooling performance and energy-saving effects of four types of roof (normal roof, phase change material [PCM] roof, cool roof, and cool PCM roof [cool roof coupled with PCM]) were investigated under a simulated sunlight. Experimental results indicate that compared with normal roof, the other three roofs are able to narrow the indoor temperature fluctuation and decrease the heat flow entering into the room. Among them, cool PCM roof gave the best energy-saving effect that can lower the indoor temperature and heat entering into rooms by 6.6 degrees C and 52.9%, respectively. Besides, the PCM location, PCM thickness, and insulation thickness exerted great impacts on the cooling performance of the roof. Placing the PCM on the internal layer beneath the extruded polystyrene (XPS) insulation board can make the indoor temperature 1.2 degrees C lower than that on the middle layer. Although thicker PCM panels or insulation boards can provide a better thermal insulation, 5 mm in PCM thickness and 20 mm in insulation thickness are enough to guarantee the indoor temperature of cool PCM roof system at a comfortable range (22 degrees C-28 degrees C) for a whole day. These findings will give guidance in designing buildings with a light and compact roof structure to decrease energy consumption and improve comfort level.