Melamine sponge (MS) has the characteristics of multilayer network structure, high porosity, adjustable pore structure, and low price, which is considered to be an ideal material for oil leakage treatment. Here, a facile, economical, environmental friendly, and one step reaction was developed to fabricate Ag nanoparticles (NPs) decorated MS composite with tannic acid (TA) as a reducing agent. By reduction reaction, the super-hydrophobic and super-oleophylic surface of the MS–TA–Ag composite was formed, demonstrating a single selectivity for oil and water. Thus, the adsorption capacity of MS–TA–Ag composites for various oils/organic solvents can reach 48~129 times its own weight and and display superior efficiency to separate oil/organic solvent from the water. In addition, the MS–TA–Ag composite has stable super-hydrophobicity and reusability. It is exciting that modified MS exhibits excellent chemical stability properties after a long processing time with strong alkali, strong acids, and salt solutions. The simple strategy provides a method for the preparation of large-scale oil spill cleaning and recovery materials.