The development of isothermal refining processes is important because of the high energy demands of crude oil separation. Membrane technology provides separation efficiency and low carbon footprint. This efficiency can be fine-tuned and enhanced by modifying the chemistry of the membrane selective layer. Herein, we describe the fabrication of membranes by interfacial polymerization using a combination of contorted fluorinated monomer bearing six fluorine atoms and trimesoyl chloride in the organic phase. A fluorinated m-phenylene diamine was added to the aqueous phase. This approach produces membranes with high surface roughness, increases their hydrophobicity and promotes the transport of hydrocarbons with high selectivity and toluene permeance (15.6 L m−2 h−1 bar−1). Successful evaluations were conducted for the fractionation of crude oil, confirming the potential for application in the petrochemical industry.