The separation of oil–water mixtures is increasingly desired due to the environmental protection and industrial production. However, the low‐oil capacity and complicated procedures in current systems remain challenging issues. Herein, porous polydimethysiloxane (PDMS) sponges are fabricated by polymerization of the prepolymer and a curing agent with the combination of NaHCO3 foaming and CO2 template method, which is novel, simple, and economical. EDS and XPS measurements prove the successful fabrication of PDMS sponges. This as‐prepared PDMS sponges show high absorption capacity (694–2513%), hydrophobicity/oleophilicity property (water contact angle and oil contact angle are 139° and 0°), and excellent thermal property. The PDMS sponges can selectively absorb a large amount of floating oils on the water surface and heavy oils under the water, and show little change of its capacities after 20 absorbing/reabsorbing cycles. © 2018 American Institute of Chemical Engineers Environ Prog, 38: S86–S92, 2019