Engineered metallodielectric nanostructures offer a new platform for controlling thermal emission in a desired manner, thus promise potential applications in passive cooling devices. Here, we present optimization design of metallodielectric multilayer structures for high-efficiency daytime radiative cooling and experimentally characterize their cooling performance. The device structure consists of alternating layers of SiO2 and PMMA on an Ag mirror, which works as a selective thermal emitter at 8-13 μm with a high reflectance for sunlight. Automated design scheme based on simulated annealing method combined with photonic-thermal analysis is developed and applied to search the optimized number and thickness of the layers. The evaluation function in the optimization process is predefined such that a net emission power would be maximized at the ambient temperature of 27 °C (300 K) under the sunlight irradiation of AM1.5G. The numerical results prove efficient radiative cooling to 3.0 °C lower than the ambient temperature, corresponding to 6.6 °C below the bare Ag mirror temperature. Based on the optimized design, the device is fabricated on an Al mirror by using reactive evaporation and spin-coating process over an area of 25 × 25 mm2. The reflectance and absorption properties of the fabricated device are characterized to demonstrate the selective thermal radiation through an atmospheric window. The equilibrium temperature of the device is also investigated to demonstrate the cooling performance under the direct sunlight irradiation.