Dense flat-sheet membranes were prepared from poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) using the casting solvents chloroform and 1,1,2-trichloroethylene. X-ray diffraction, tapping mode atomic force microscopy (TM-AFM), and contact angle studies were used to characterize the membranes. The surface energy and the solubility parameters of the PPO membranes were determined from the measured contact angles and compared with the predicted ones from the group contribution method. Swelling experiments and pervaporation separation of methanol from its mixture with ethylene glycol over the entire range of concentration, 0-100%, were conducted using these membranes. Flory-Huggins theory was used to predict the sorption selectivity. The results are discussed in terms of the solubility parameter approach and as function of the morphological characteristics of the membranes. It was found that PPO membranes prepared with chloroform exhibited better pervaporation performance than PPO membranes prepared with 1,1,2-trichloroethylene.