Mesoporous graphene with a surface area of 306 m2 g−1 was synthesized by employing CaCO3 microspheres as hard templates. By surface modification with polydimethylsiloxane (PDMS) through chemical vapor deposition, the wettability of as-treated mesoporous graphene can be tailored to be superhydrophobic to water while superoleophilic to oils. The deposition of the low-surface-energy silicon-coating originated from PDMS pyrolysis on porous graphene was confirmed by X-ray photoelectron spectroscopy. As a result of its porous structures and excellent surface superhydrophobicity, the PDMS-treated mesoporous graphene exhibits good selectivity, excellent recyclability, and good absorption performance (up to 66 g g−1) for a wide range of oils and organic solvents. Thus, leading to potential use in a variety of applications such as water treatment and purification as well as cleanup of oil spills.