The leakages of a large number of organic solvents and oil spills not only cause extensive economic losses, but also destroy the ecological environment. However, there were few studies on the surface engineering of adsorption materials for efficient oil-water separation in complex environments. In this research, through surface engineering, the polymer-based foam exhibited high efficiency oil-water separation performance in different pH environments. Hydrophobic groups were introduced onto the surface of nano-sized SiO2 particles via hydrolysis and polycondensation reactions, and then the modified SiO2 was loaded on the foam. After modification, the water contact angle of the modified foam increased from 116.4° to 152.5°, and the oil-water separation performance was obviously enhanced. The oil removal rate of the modified foam remained above 96%. The highest capacity of petroleum diesel was 33.4 g-1, which was much higher than other similar adsorption materials. In addition, the modified foam maintained good hydrophobicity and oil removal rate in a wide pH range. The efficient oleophilic and hydrophobic foam prepared by combining green physical foaming with surface engineering was expected to be widely used in large-scale organic solvent recovery and oil leakage emergency treatment.