Hierarchical functional organic-inorganic hybrid particles for versatile control of surface wettability have attracted much attention in a wide range of applications from makeup cosmetics to anti-smudging optoelectronic devices. In this study, superhydrophobic and oleophobic organic-inorganic hybrid particles were prepared by a simple and systematic fabrication strategy using the synergistic combination of commonly available silica particles and polydimethylsiloxanes (PDMSs) with hydrophobic chain ends. Various types of PDMSs with different chain lengths and chemical structures were surface-grafted to silica microparticles through facile physical dispersion and subsequent thermal treatment to form hydrogen bonds or covalent bonds between the inorganic silica and organic PDMS polymers and thus induce a core-shell structure for the hybrid particles, which imparts superhydrophobicity and oleophobicity to the surface of silica particles. The prepared PDMS-coated silica hybrid particles with long PDMS chains exhibited a water contact angle of 151.2° and an oil contact angle of 15.2° due to the rough surface morphology and hydrophobic long-chain effects. Furthermore, the resulting organic-inorganic hybrid particles were thermally stable up to 420 °C. This controlled approach endowed the organic-inorganic hybrid particles with both superhydrophobic and oleophobic surfaces and, therefore, these particles were proven to be suitable for waterproof applications.