Radiative cooling (RC) is a carbon-neutral technology that uses thermal radiation to dissipate heat from the Earth's surface into cold outer space. It has gained significant attention due to its potential to reduce energy consumption and greenhouse gas emissions from conventional cooling systems. Materials innovation is key to fully exploiting RC's potential. This review focuses on the design strategies, intrinsic properties, structural formations, and performance improvement of RC materials. The main types of RC materials—static-homogeneous, static-composite, dynamic, and multifunctional—are systematically overviewed. Future trends, challenges, and potential solutions are discussed to provide a roadmap for advanced RC materials. RC materials are designed to have high emissivity for heat dissipation and low absorptivity for solar radiation. Key intrinsic properties include band gaps, refractive indices, and molecular vibrations. Static-homogeneous materials, such as polymers, inorganic solids, and gases, are simple to fabricate and effective for nighttime cooling. Daytime RC materials require high emissivity in the long-wave infrared (LWIR) range and high solar reflectance. Porous polymers, inorganic particles, and nanofibers are used to achieve these properties. For example, hierarchically porous P(VdF-HFP) coatings and cooling wood exhibit high solar reflectance and LWIR emissivity. Static-composite materials, including inorganic-inorganic, organic-organic, and organic-inorganic hybrids, offer enhanced performance. Inorganic-inorganic composites, such as metal-based and ceramic-based materials, provide high solar reflectance and LWIR emissivity. Metal-based composites, like those with SiO₂ and HfO₂ layers, achieve high reflectance and sub-ambient cooling. Ceramic-based composites, such as glass-based coatings and all-ceramic aerogels, exhibit excellent stability and performance. Organic-organic composites, including cellulose and silk-based materials, offer flexibility and biodegradability, with high LWIR emissivity due to molecular vibrations. Dynamic and multifunctional materials are also explored for their ability to adapt to changing conditions and perform multiple functions. The review highlights the importance of material design in achieving efficient and sustainable RC technologies, emphasizing the need for further research and development in this field.Radiative cooling (RC) is a carbon-neutral technology that uses thermal radiation to dissipate heat from the Earth's surface into cold outer space. It has gained significant attention due to its potential to reduce energy consumption and greenhouse gas emissions from conventional cooling systems. Materials innovation is key to fully exploiting RC's potential. This review focuses on the design strategies, intrinsic properties, structural formations, and performance improvement of RC materials. The main types of RC materials—static-homogeneous, static-composite, dynamic, and multifunctional—are systematically overviewed. Future trends, challenges, and potential solutions are discussed to provide a roadmap for advanced RC materials. RC materials are designed to have high emissivity for heat dissipation and low absorptivity for solar radiation. Key intrinsic properties include band gaps, refractive indices, and molecular vibrations. Static-homogeneous materials, such as polymers, inorganic solids, and gases, are simple to fabricate and effective for nighttime cooling. Daytime RC materials require high emissivity in the long-wave infrared (LWIR) range and high solar reflectance. Porous polymers, inorganic particles, and nanofibers are used to achieve these properties. For example, hierarchically porous P(VdF-HFP) coatings and cooling wood exhibit high solar reflectance and LWIR emissivity. Static-composite materials, including inorganic-inorganic, organic-organic, and organic-inorganic hybrids, offer enhanced performance. Inorganic-inorganic composites, such as metal-based and ceramic-based materials, provide high solar reflectance and LWIR emissivity. Metal-based composites, like those with SiO₂ and HfO₂ layers, achieve high reflectance and sub-ambient cooling. Ceramic-based composites, such as glass-based coatings and all-ceramic aerogels, exhibit excellent stability and performance. Organic-organic composites, including cellulose and silk-based materials, offer flexibility and biodegradability, with high LWIR emissivity due to molecular vibrations. Dynamic and multifunctional materials are also explored for their ability to adapt to changing conditions and perform multiple functions. The review highlights the importance of material design in achieving efficient and sustainable RC technologies, emphasizing the need for further research and development in this field.