Eco-friendly oil–water separation substrates are mostly recommended in the present context of the world. In the present work, biodegradable and more economical ultrahydrophobic composite material was synthesized by sol–gel method using silica nanoparticles (SiO2) and poly (methyl methacrylate-co-ethyl acrylate) polymer (PMMA) with 1H,1H,2H,2H Perfluorooctyltrichlorosilane (PFOTS) coupler, and coated on 40-grade cellulose filter paper with a dip-coating method. As-prepared surfaces achieved static contact angle more than 175° and sliding angle 3.8°. The microstructure and chemical composition of ultrahydrophobic filter paper were characterized by scanning electric microscopy (SEM), X-ray spectroscopy (EDX), and Flourier transformation infrared spectroscopy (FTIR), respectively. The coated filter paper accomplished 98% oil–water separation efficiency by filtering different oils. Besides, the SiO2 nanoparticles were enhanced the thermal and UV aging resistance. The coated surfaces also showed excellent chemical inertness, and mechanical durability tested. This research work can be employed yet for domestic and industrial applications at a large scale for oil–water separation and self-cleaning.