Materials with high performance for oil-water separation play an important role for enhancing the oil recovery efficiency and management of environmental contaminants. This thesis focuses on the preparation of super-hydrophobic polymers for oil-water separation by using commercial starting materials. Two polymer sponges, i.e., ternary silicone sponge and melamine sponge were prepared via the in-situ polymerization and surface modification techniques, respectively, and their mechanical, adsorption and thermal properties were studied. Major findings are summarized as follows: Ternary silicone sponge derived from methyltrimethoxysilane (MTMS), dimethyldimethoxysilicane (DMDMS) and tetraethylorthosilicate (TEOS) was prepared by using a simple sol-gel process. The effects of TEOS on the morphology and mechanical properties of sponge were studied. The developed silicone sponge showed a superhydrophobic and superlipophilic behavior, high adsorption capacity for a various organic solvents and oils with stable cyclic operations. The excellent thermal stability of sponge made the material possibly to be used under the high temperature conditions. A simple and efficient method for the chemical modification of melamine sponge was developed by using MTMS and TEOS as modifier. The modified-melamine sponge had an ultra-high oil absorption capacity for commonly organic solvents and oils without obvious dissolution/swelling. With assistance of a vacuum pump, the material can be employed for the continuous separation of octane and crude oil from corresponding water mixtures. By using the modified melamine sponge as key material, an experimental setup was established to demonstrate the feasibility of collecting oil and chemical spills from water surface. The research was further extended to design a prototype oil collector with capability to clean oily spills, and its applicability was verified.