Daytime radiative cooling materials exhibit huge potential for sustainable development, which can reflect sunlight and radiate heat to outer space in the main atmospheric window without energy consumption. Recently, polymer-based nanofiber membranes have been fabricated for radiative cooling, because of their easy processing and ideal optical performance. However, there exist big challenges in fabricating low-cost and environmentally friendly daytime radiative cooling materials for large-scale practical applications. In this work, we demonstrate a novel poly(vinyl alcohol)@silica (PVA@SiO2) composite membrane via typical electrospinning technology and a simple coating process. The resultant composite membrane exhibits spectral selectivity with high sunlight reflectance of ∼95.0 % as well as a mid-infrared emissivity of ∼90.2 %, UV protection, and hydrophobicity, endowing its excellent daytime radiative cooling effect with a temperature drop of ∼8.0 °C. The as-obtained membranes exhibit some promising future for the potential large-scale application of radiative cooling technology for energy savings.