Abstract Here, we report a selective multilayer emitter for eco-friendly daytime passive radiative cooling. The types of materials and thickness of up to 10 layers of the multilayer structure are optimized by a genetic algorithm. The passive radiative cooler is designed to mainly target low solar absorption, which allows sub-ambient cooling under direct sunlight. We used a custom objective function in the solar region to achieve high-performance daytime radiative cooling to minimize solar absorption. The designed structure minimizes solar absorption with an average absorptivity of 5.0% in the solar region (0.3–2.5 μm) while strongly emitting thermal radiation with an average emissivity of 86.0% in the atmospheric transparency window (8–13 μm). The designed and fabricated structure achieves daytime net cooling flux of 84.8 W m⁻² and 70.6 W m⁻², respectively, under the direct AM 1.5 solar irradiation (SI) (total heat flux of 892 W m⁻² in the 0.3–2.5 μm wavelength region). Finally, we experimentally demonstrate a passive radiative cooling of the fabricated selective emitter through a 72-hour day-night cycle, showing an average and maximum temperature reduction of 3.1 °C and 6.0 °C, respectively. Our approach provides additional degrees of freedom by designing both materials and thickness and thereby is expected to allow high-performance daytime radiative cooling.