Three-dimensional (3D) porous absorbents have attracted significant attention in the oily wastewater treatment technology due to their high porosity and elasticity. Given their amphiphilic surface, they have a propensity to simultaneously absorb water and oil, which restricts their range of applications. In this study, a reduced graphene oxide and titanium dioxide nanocomposite (rGO/TiO2) was used to fabricate an ultrahydrophobic melamine sponge (MS) through interfacial modification using a solution immersion technique. To further modify it, polydimethylsiloxane (PDMS) was grafted onto its surface to establish stronger covalent bonds with the composite. The water contact angle of the sponge (rGO/TiO2/PDMS/MS) was 164.2°, which satisfies the condition for ultrahydrophobicity. The evidence of its water repellency was demonstrated by the Cassie–Baxter theory and the lotus leaf effect. As a result of the increased density of rGO/TiO2/PDMS/MS, it recorded an initial capacity that was 2 g/g lower than the raw MS for crude oil absorption. The raw MS retained 53% of its initial absorption capacity after 20 cycles of absorption, while rGO/TiO2/PDMS/MS retained 97%, suggesting good recyclability. Excellent oil and organic solvent recovery (90%–96%) was demonstrated by rGO/TiO2/PDMS/MS in oil–water combinations. In a continuous separation system, it achieved a remarkable separation efficiency of 2.4 × 106 L/(m3·h), and in turbulent emulsion separation, it achieved a demulsification efficiency of 90%–91%. This study provides a practical substitute for massive oil spill cleaning.