In recent years, many parts of the world have researched the transition to renewable energy, reducing energy consumption and moving away from fossil fuels. Among the studies to reduce energy consumption, passive radiative cooling can reduce the energy used for building cooling, and to improve this, the optical properties of atmospheric window emissivity and solar reflectance must be increased. In this study, hollow yttrium oxide (H-Y2O3) was fabricated using melamine formaldehyde (MF) as a sacrificial template to improve the optical properties of passive radiative cooling. We then used finite-difference time-domain (FDTD) simulations to predict the optical properties of the fabricated particles. This study compares the properties of MF@Y(OH)CO3 and H-Y2O3 particles derived from the same process. H-Y2O3 was found to have a solar reflectance of 70.73% and an atmospheric window emissivity of 86.24%, and the field tests revealed that the temperature of MF@Y(OH)CO3 was relatively low during the daytime. At night, the temperature of the H-Y2O3 film was found to be 2.6 °C lower than the ambient temperature of 28.8 °C. The optical properties and actual cooling capabilities of the particles at each stage of manufacturing the hollow particles were confirmed and the cooling capabilities were quantified.