Ethylene glycol (EG) is widely used in various economic and industrial fields. The de-mand for its efficient separation and recovery from water is constantly growing. To improve the pervaporation characteristics of a poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) membrane in dehydration of ethylene glycol, the modification with graphene oxide (GO) nanoparticles was used. The effects of the introduction of various GO quantities into the PPO matrix on the structure and physicochemical properties were studied by Fourier-transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopies, scanning electron (SEM) and atomic force (AFM) microscopies, thermogravimetric analysis (TGA), swelling experiments, and contact angle measurements. Two types of membranes based on PPO and PPO/GO composite were developed: dense membranes and supported membranes on a fluoroplast substrate (MFFC). Transport properties of the developed membranes were evaluated in the pervaporation dehydration of EG in a wide concentration range (10–90 wt.% and 10–30 wt.% water for the dense and supported membranes, respectively). The supported PPO/GO(0.7%)/MFFC membrane demonstrated the best transport properties in pervapo-ration dehydration of EG (10–30 wt.% water) at 22 ^◦C: permeation flux ca. 15 times higher compared to dense PPO membrane—180–230 g/(m ^2·h)), 99.8–99.6 wt.% water in the permeate. The membrane is suitable for the promising industrial application.