Passive radiative cooling is an energy-efficient method that reduces indoor temperature and cooling load in buildings, thus contributing to significant energy savings. This study investigates the thermal performance of the passive radiative cooling-based cool roof (PRC-CR) based on experimental and numerical analysis in terms of indoor air temperature and space cooling load indicators. Two experiment rooms constructed from concrete are developed with an indoor air temperature control system. One is the PRC-CR room with the roof covered by a passive radiative cooling metamaterial and the other is the reference room with a concrete roof. Long-term testing results in Hefei show that the indoor air temperature of the PRC-CR room is 5.5 °C lower in maximal and 1.8 °C lower on average than that of the reference room in summer when the indoor air temperature control system is off. Besides, when the indoor air temperature control system is switched on, the PRC-CR room achieves a 29.1% reduction in daily cooling load in summer and a 4.1% increase in daily heating load in winter, which suggests that passive radiative cooling can indeed save energy in cooling season (i.e., hot season) but cause overcooling in heating season (i.e., cold season). In addition, a simulation building model is developed to further investigate the effect of the PRC-CR on the energy consumption of buildings in different locations. The predicted results show that PRC-CR reduces the total load of buildings in cooling load prevailing regions (e.g., tropical zones, subtropical zones, and the vast majority of warm temperate zones), while increasing the total load of buildings in heating load dominant regions (e.g., most middle temperate zones, cold temperate zones, and plateau climate zones). In summary, this work demonstrates both the positive and negative effects of PRC-CR, providing valuable insights into PRC-CR applications.