This study focuses on preparation of mulberry-like CaCO3/SiO2 composite particles with a mechanochemical method and their application in superhydrophobic films. Silicon dioxide nanoparticles were adhered to calcium carbonate microparticles to form mulberry-like composite particles through vigorous stirring, which prevented agglomeration of silicon dioxide nanoparticles and maintained their nanocharacteristics. Then, hexamethyldisilazane was employed for hydrophobic modification of the mulberry-like CaCO3/SiO2 composite particles. The effect of CaCO3/SiO2 mass ratios, stirring speed, reaction temperature, and amount of modifying reagent on morphology and lipophilicity of composite particles was studied. Moreover, the superhydrophobic films with excellent film properties were obtained by through combination of mulberry-like CaCO3/SiO2 hydrophobic composite particles and RTV silicon rubber. The water contact angle and sliding angle of the superhydrophobic surface were measured to be 170 ± 2.5 ◦ and 4◦, respectively. This approach proves to be ideal for substantial improvement of the self-cleaning property of RTV silicon rubber
anti-pollution flashover coating.