A superhydrophobic and superoleophilic porous composite was successfully prepared via a polydopamine-assisted surface coating of MIL-53(Fe) and 1-dodecanethiol (DDT) on a melamine formaldehyde (MF) sponge. The as-prepared sponge composite (MIL-DDT@MF) has a high water contact angle (WCA) of 151.8 degrees, which is probably attributed to both the rough surface derived from in situ growth of MIL-53 nanocrystals and the low surface energy due to grafting of hydrophobic 1-dodecanethiol. The MIL-DDT@MF sponge can effectively absorb oil or organic solvent with an absorption capacity of up to 54.1 (for petroleum) to 120.2 (for chloroform) times its own weight. In addition, the MIL-DDT@MF sponge retained a high absorption capacity and maintained approximately 78% of its original value after 50 cycles of reuse. Moreover, the MIL-DDT@MF sponge can selectively absorb the oil/organic solvent from water and achieve continuous oil-water separation. The separation efficiency of n-hexane, dichloromethane, and crude oil from water or seawater can reach above 95%. The superhydrophobic and superoleophilic MIL-DDT@MF sponge has potential as a promising absorbent for treatment of oily wastewater.