Processes for olefin/paraffin separation utilizing porous, hydrophobic poly(ether ether ketone) (PEEK) membranes are provided. In accordance with an exemplary embodiment, a process for olefin/paraffin separation comprises providing a porous membrane formed of PEEK polymer functionalized with hydrophobic groups, the porous membrane having a first surface and a second surface. The first surface of the porous membrane is contacted with a feed comprising an olefin and a paraffin and a permeate is caused to flow from the second surface of the porous membrane. The permeate has a concentration of the paraffin that is higher than a concentration of the paraffin of the feed.