The work aims to improve the transmittance, scratch resistance and weatherability of SiO2 antireflection coatings used in photovoltaic/optothermal field. The SiO2 with core-shell structure was prepared with polyacrylic acid (PAA, Mw ~ 3000) as template. PAA template was removed by centrifugation washing to form SiO2 hollow spheres. The hollow spheres were dispersed in ethanol to form a sol. Then the sol was mixed with the acid-catalyzed sol to form a composite sol. Finally, the SiO2 hollow sphere antireflection coating was prepared on the slide glass dipping, filming and sintering. The microstructure of the hollow spheres and the surface morphology of the antireflection coatings were characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM) respectively. The transmittance of the antireflection coatings was measured by anultroviolet-visible spectrophotometer. The scratch resistance and weatherability of the antireflection coatings were measured through the pencil hardness test and the moisture-heat resistance test (HAST) respectively. TEM measurements showed that the prepared hollow SiO2 hollow spheres had a complete structure with uniform wall thickness. SEM images showed that the antireflection coatings were flat and smooth. When the ratio of SiO2 hollow sphere sol to acid catalyzed sol was 9:1, the peak value of antireflection coating transmittance was 98.1%, the scratch resistance hardness was 5 H, and the attenuation rate of transmittance became 98.1% of the initial value after HAST test. Therefore, hollow spheres prepared by centrifugal washing to remove PAA templates have a higher void ratio than that prepared by the sintering template removal method. The SiO2 hollow spheres antireflection coatings prepared by being mixed with acid-catalyzed sol have high porosity, low refractive index and improved antireflection coatings transmittance. At the same time, the closed pore structure makes antireflective coating flat and smooth, and such a coating has better scratch resistance and weatherability than the coatings with open-cell structure. It has an important application value in the outdoor solar photovoltaic/optothermal antireflection.