Poor mechanical stability of superhydrophobic coating limits its practical application. In this work, robust superhydrophobic organically modified silicate (ORMOSIL) hybrid coatings were fabricated on wood surface by a chemical-assembly engineering induced by click reaction of PMHS. The superhydrophobic ORMOSIL coating was hybridized from poly(methylhydrogen)siloxane (PMHS), tetravinyltetramethylcyclotetrasiloxane (V4), and silica nanoparticles (SNPs). The click reaction between PMHS and SNPs built a chemically bonded rough surface with very low surface energy, while click reaction between PMHS and V4 resulted in a strong glue of adjacent SNPs, endowing ORMOSIL hybrid coatings with good mechanical stability. Chemical-assembly engineering afforded ORMOSIL coatings superhydrophobicity, self-cleaning property, and good robustness, and the unique physical characteristic of ORMOSIL also gave superhydrophobic coatings excellent resistance to UV light, high and low temperature, and humid and salt mist environments. Finally, chemical-assembly engineering had been demonstrated to be applicable in fabrication of superhydrophobic coating on various substrates containing hydroxyl groups and various nanoparticles could be applied to replace SNPs.