Superhydrophobic SiO2 layers with a micro-nano hierarchical surface structure were prepared. SiO2 layers depositedvia an electrospray method combined with a sol-gel chemical route were rough on the microscale. Au particles were decoratedon the surface of the microscale-rough SiO2 layers by use of the photo-reduction process with different intensities (0.11-1.9 mW/cm2) and illumination times (60-240 sec) of ultraviolet light. With the aid of nanoscale Au nanoparticles, this consequentlyresulted in a micro-nano hierarchical surface structure. Subsequent fluorination treatment with a solution containingtrichloro(1H,2H,2H,2H-perfluorooctyl)silane fluorinated the hierarchical SiO2 layers. The change in surface roughness factorwas in good agreement with that observed for the water contact angle, where the surface roughness factor developed as ameasure needed to evaluate the degree of surface roughness. The resulting SiO2 layers revealed excellent repellency towardvarious liquid droplets with different surface tensions ranging from 46 to 72.3mN/m. Especially, the micro-nano hierarchicalsurface created at an illumination intensity of 0.11mW/cm2 and illumination time of 60 sec showed the largest water contactangle of 170o. Based on the Cassie-Baxter and Young-Dupre equations, the surface fraction and work of adhesion for the micro-nano hierarchical SiO2 layers were evaluated. The work of adhesion was estimated to be less than 3×10−3N/m for all the liquiddroplets. This exceptionally small work of adhesion is likely to be responsible for the strong repellency of the liquids to themicro-nano hierarchical SiO2 layers.