A huge concern on global climate/energy crises has triggered intense development of radiative coolers (RCs), which are promising green‐cooling technologies. The continuous efforts on RCs have fast‐tracked notable energy‐savings by minimizing solar absorption and maximizing thermal emission. Recently, in addition to spectral optimization, ceramic‐based thermally insulative RCs are reported to improve thermoregulation by suppressing heat gain from the surroundings. However, a high temperature co‐firing process of ceramic‐based thick film inevitably results in a large mismatch of structural parameters between designed and fabricated components, thereby breaking spectral optimization. Here, this article proposes a scalable, non‐shrinkable, patternable, and thermally insulative ceramic RC (SNPT‐RC) using a roll‐to‐roll process, which can fill a vital niche in the field of radiative cooling. A stand‐alone SNPT‐RC exhibits excellent thermal insulation (≈0.251 W m−1 K−1) with flame‐resistivity and high solar reflectance/long‐wave emissivity (≈96% and 92%, respectively). Alternate stacks of intermediate porous alumina/borosilicate (Al2O3‐BS) layers not only result in outstanding thermal and spectral characteristics, causing excellent sub‐ambient cooling (i.e., 7.05 °C cooling), but also non‐shrinkable feature. Moreover, a perforated SNPT‐RC demonstrates its versatility as a breathable radiative cooling shade and as a semi‐transparent window, making it a highly promising technology for practical deployment in energy‐saving architecture.

Radiative cooling technology is extensively researched as a green technology, leveraging outer space as a thermodynamic resource. Recently, integrating thermoelectric generators (TEGs) and radiative coolers (RCs) are proposed to generate power using the temperature difference between the ambient and the radiative cooler. However, current TEG‐RC systems only utilize one thermodynamic resource, resulting in suboptimal efficiency. It proposes a parabolic mirror‐assisted TEG‐RC system that fully utilizes both the Sun and outer space as thermodynamic resources. The system places the hot side of the TEG, covered by a solar absorber (SA), at the focal point of the parabolic mirror, while the RC is located on the cold side of the TEG. Theoretical and experimental results reveal the optimal ratio between the RC and SA sizes to balance the power mismatch between cooling and heating powers. It also finds that the number of TEG stacks significantly affects power generation efficiency and determines the optimal number. Outdoor measurements demonstrate exceptional power generation during the daytime, which is an unprecedented achievement. This study also demonstrates the further enhancement in power generation efficiency when the proposed system is integrated with concentrated solar cells instead of the SA.