One of the most pervasive environmental issues is water contaminated with oil or organic solvents; this global challenge calls for emerging materials that could effectively separate oil or organic solvents from water. Here, such a material is presented by integrating 3D porous graphene foam (GF) with a smart pH-responsive surface, showing switchable superoleophilic and superoleophobic properties in response to the medium pH. The key chemistry applied in this study is to modify the 3D porous GF with an amphiphilic copolymer containing a block of poly(2-vinylpyridine) and polyhexadecyl acrylate (P2VP-b-PHA), resulting in a smart GF (ss-GF) with an either superoleophilic or superoleophobic surface at different medium pH. The as-designed ss-GF can effectively absorb oil or organic solvents from the aqueous media by using its superoleophilic surface at pH of 7.0, and it can also completely release the adsorbates when the pH is switched to 3.0 (and the surface of ss-GF is therefore shifted to superoleophobic); with a continuous operation of many cycles (e.g., >10). Furthermore, the as-designed ss-GF shows superior absorption capacity for oil and organic solvent, with a high capacity of approximate to 196 times of the weight relative to that of the pristine ss-GF. The present work suggests encouraging applications of the ss-GF to water-oil and water-organic solvent separation.