A new facile approach for preparing two nonfluorinated hybrid organic–inorganic siloxane/polydimethylsiloxane nanocomposite coatings for cotton fabrics is presented using two distinct silylating agents. The first coated fabric was prepared predominantly via trimethylsilyl modification using hexamethyldisilazane (HMDS) while higher amounts of trimethoxy(octadecyl)silane (TMOS) further enhanced the superhydrophobicity of the second coating matrix. Unlike HMDS with substituted silyl (Me₃Si) groups, TMOS consists of hydrolysable trimethoxy silyl ((MeO)₃Si) chemical groups that allowed for the formation of nanosilica with Si–O–Si linkages needed to foster stable coatings. After characterization and testing, these coated fabrics demonstrated varying responses to harsh solvents and thermal conditions. Both sets of coated fabrics exhibited unique capacities for self-cleaning and oil–water separation as superhydrophobic filters due to (a) their low surface energy silylated hybrid polysiloxane chemical groups, (b) their highly reduced surface wettability and (c) nanopatterned surface morphologies. In this study, coated superhydrophobic cotton fabrics revealed a higher static aqueous contact angle of more than 150° and sliding hysteresis angle of less than 5°. Coated fabrics with 30 mg TMOS/10 mg HMDS (CMF3) and 30 mg HMDS/10 mg TMOS (CTF3) exhibited optimal superhydrophobicity. Both fabrics also retained percentage separation efficiencies over 90% for both chloroform–water and toluene–water mixtures. However, CTF3 displayed with a recorded separation efficiency less than 90° after five filtration cycles.