Carbon foams have been applied widely in energy, environment and catalyst, but it is still challengeable to exploit simple and facile strategies to construct carbon foams with well-developed three-dimensional connected pore structure. In the present paper, we report a novel method to synthesize carbon foam by direct cross-linking of styrene-butadiene rubber-based powder puff (SBR). The high-density cross-linking bonds can address the thermal instability of SBR, and then endow it with rigid macromolecular framework and carbonizability. Therefore, the obtained carbon foam well inherits the micromorphology from SBR and incorporates the structural characteristics of light weight, honeycomb-like pore structure and tunable surface morphology. Owing to these structural advantages, the obtained carbon foam presents superior oil-water separation performance and Na+ storage property. For example, the carbon foam has high adsorption capacities of pump oil and other solvents (300-500%), and it can be recovered to the original state by combustion. In addition, the reversible Na+ storage capacity of carbon foam can reach 220 mAh g(-1).