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This work elucidates the influence of graphene (G) and graphene oxide (GO) content on the desalination performance and scaling characteristics of G/polyvinylidene fluoride (G/PVDF) mixed matrix and GO/PVDF composite‐skin membranes, applied in a direct contact membrane distillation process (DCMD). Inclusion of high quality, nonoxidized, monolayered graphene sheets as polymer membrane filler, and application of a novel GO/water‐bath coagulation method for the preparation of the GO/PVDF composite films, took place. Water permeability and desalination tests via DCMD, revealed that the optimal G content was 0.87 wt%. At such concentration the water vapor flux of the G/PVDF membrane was 1.7 times that of the nonmodified reference, while the salt rejection efficiency was significantly improved (99.8%) as compared to the neat PVDF. Similarly the GO/PVDF surface‐modified membrane, prepared using a GO dispersion with low concentration (0.5 g/L), exhibited twofold higher water vapor permeate flux as compared to the neat PVDF, but however, its salt rejection efficiency was moderate (80%), probably due to pore wetting during DCMD. The relatively low scaling tendency observed for both G and GO modified membranes is primarily attributed to their smoother surface texture as compared to neat PVDF, while scaling is caused by the deposition of calcite crystals, identified by XRPD analysis. POLYM. ENG. SCI., 59:E262–E278, 2019. © 2018 Society of Plastics Engineers