SiO2 is the hotspot radiative cooling material due to its selective radiation or the Mie resonance effect generated by micro/nanospheres of a specific size. Herein, we demonstrate the modulation of the IR emissivity of the intrinsic SiO2 at the atm. window by doping Mg2+ in nanoporous SiO2 nanoparticles via a modified stober method. The effects of the Mg-doping on the crystallinity, morphol., IR emissivity of the nanoparticles and the radiative cooling properties of the corresponding coatings are investigated. Results show that the Mg-doping at a level of 0.226-2.26 % can induce cristobalite nanocrystals after sintering at 1000 °C, transform the morphol. from spheres to irregular nanoporous particles, and improve the IR emissivity up to 0.96. XPS proves the formation of Mg-O bonds and the change of the binding energy of Si 2p and O 1s, supporting the successful doping of Mg2+ in the lattice of SiO2. All-inorganic Mg-doped SiO2 coatings on FTO substrates are prepared via tape casting, which exhibit rough and porous microstructure and high solar reflectivity up to ∼86 %, with the thickness of ∼90 μm. The Mg-doping improves the radiative cooling capacity of the coatings obviously, and the best temperature reduction of 17.8 °C compared with the empty space is achieved, 3-5 °C lower than the pure SiO2 coating and 4.5 °C lower than the com. SiO2 coating. Our work offers an effective way to modulate the IR emission of emitter, enriching the tech. measures to improve the overall performance of the sub-ambient radiative cooling devices.