Serious damage caused by oily wastewater makes the development of efficient superhydrophobic and superoleophilic materials for oil/water separation processes critical and urgent. Herein, durable superhydrophobic nanometer-scale TiO2 grains with low-surface-energy substance composite-modified materials were fabricated by using a cost-effective and facile synthesis method for the gravity-driven separation of oil/water mixtures under harsh conditions. Different substrates, such as sawdust, wheat straw, cotton, sponge and fabric, were applied for superhydrophobic surface preparation, and various low-surface-energy reagents could interact with deposited TiO2 nanoparticles, including cetylamine, dodecanethiol, stearic acid and HDTMS. The resultant materials showed superhydrophobic properties with a water contact angle (WCA) higher than 150.8°. The separation of various oil/water mixtures with high efficiency and purity was acquired by using the as-prepared sponge. More importantly, the coated sponge exhibited good resistance to various harsh environmental solutions. Moreover, its superhydrophobicity also remained even after 12 months of storage in air or 10 cycles of abrasion. The durable superhydrophobic coating prepared in this work could be practically used for the highly efficient separation of oil/water mixtures under various harsh conditions.