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.