Removal of aromatic compounds from fuel is an essential requirement in new environmental policies. In the present study, poly(vinyl alcohol)/graphene oxide (GO) mixed matrix membranes were prepared and applied to the separation of toluene from iso‐octane by pervaporation, considering the similarity and interaction between graphene and aromatics. The effects of crosslinking and GO content on separation efficiency have been investigated in detail. Owing to the high affinity of GO with toluene through s and π bonds, the selectivity of the membranes was increased by incorporating a low amount of GO. The results also indicated that noncrosslinked membranes have higher selectivity and permeation flux due to higher crystallinity and also have lower mechanical properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45853.