Superhydrophobic and oleophilic sponges have been demonstrated as promising candidates for oil/water separation. However, there are still challenges in large-scale fabrication of superhydrophobic sponges with low cost and feasible method for industrial applications. Herein, we report a superhydrophobic and oleophilic melamine sponge functionalized by a uniform polydimethylsiloxane (PDMS) film that can be easily coated onto the sponge skeleton through UV-assisted thiol-ene click reactions. The PDMS films are characterized by a hierarchically striped microstructure with an average distance less than 2 μm. Because of the striped microstructure and the hydrophobic property of silicone, a high contact angle of 156.2° was achieved. Importantly, the interconnected open-cell structure of the melamine sponge was preserved by adapting the thickness of the PDMS film. The PDMS-coated melamine sponge exhibited a desirable absorption capacity of 103-179 times its own weight with oils and organic solvents. The excellent mechanical properties of melamine and the flexibility of PDMS enable the PDMS-coated melamine sponges to be squeezed repeatedly without collapsing. This study offers a robust and effective approach in large-scale preparation of a superhydrophobic sponge for large-scale oil spill containment and environmental remediation by the inexpensive commercial polymethylvinylsilicone and facile dip-coating/UV-curing method.