In this paper, A novel ZnO/SiO2 composite superhydrophobic coating was obtained by magnetron sputtering and surface fluoridation of zinc oxide (ZnO) and silicon dioxide (SiO2) particles at different nanoscales. And the effect of different fluoride modifiers on the anti-icing performance of the novel ZnO/SiO2 composite superhydrophobic coating was studied. Water contact Angle (CA), rolling Angle (SA), microstructure of the coating and the change of chemical bond before and after fluorination were analyzed by optical contact angle measuring instrument, scanning electron microscope (SEM) and Fourier transform infrared spectrometer (FTIR). Icing time of the coating and the adhesion strength of the ice on the coating surface in high humidity and low temperature were tested by self-made icing device and digital display tension meter. The results show that the particle arrangement of composite ZnO and SiO2 nanoparticles prepared by magnetron sputtering is regular, and the mixing of the two different size particles makes the coating surface show multi-cluster micro/nano secondary structure, which can reduce the adhesion of the droplets to the surface. Heptafluorodecyl triethoxysilane (FAS-17), polydimethylsiloxane (PDMS), dodechoheptyl propyl trimethoxysilane (G502) and hexyl trimethoxysilane (HDTMS) were selected to modify the coating surface as a whole respectirely. Among them, FAS-17 modified coating surface had the best anti-icing effect, the liquid-gas composite contact area ratio reached 94.38%, the contact angle and rolling angle reached the best, was 164° and 3°, respectively, and the surface ice adhesion strength decreased to 3.8 kPa. Under the conditions of 60% humidity, -2 -10 and -20 ℃, respectively, the delaying freezing time of the coating was 2 446, 1 604 and 137 s. It is concluded that a new type of composite superhydrophobic coating with cluster structure can be obtained by magnetron sputtering and whole surface modification of ZnO and SiO2 nanoparticles with different nanoscale. The surface fluoridation of FAS-17 ethanol solution can significantly improve the superhydrophobic properties of the coating.