Octadecyltrimethoxysilane (OTMS) was introduced to hydrophobically modify the surface of nano-silica, then the modified lipophilic silica was added into the silicone resin (SI) as a superhydrophobic modifier. Subsequently, SI/OTMS-SiO2 functional composite coating was constructed with the polyethylene (PE) as a substrate utilizing a two-step cure method. The accurate chemical structure of the modified nano-silica and the composite coating were determined by means of the chemical structure characterization, resulting that OTMS was successfully integrated onto SiO2 and OTMS-SiO2 uniformly loaded onto the silicone surface, as well as the composite coating was obtained. Then, the effects of the introduction of modified SiO2 on the surface roughness of the composite coating were characterized by SEM and AFM, and the mechanism of constructing a superhydrophobic coating was invested. On this basis, the effects of the modified SiO2 structure on the superhydrophobic properties, wear resistance, thermal stability and other properties of PE films coated with SI/OTMS-SiO2 superhydrophobic coating were systematically investigated, and the microscopic morphology of the composite coating surface and its hydrophobic properties were studied.