The influence of a plasticizer in the form of the residual solvent dimethylacetamide on pervaporation and sorption properties of membranes based on poly(phenylene isophtalamide) (PA) was investigated. To analyze the influence of the plasticizer on membrane transport properties, pervaporation of binary water–ethyl acetate mixtures was studied. The method of sorption calorimetry was used to investigate water sorption properties of the studied membranes and PA powder. Moreover, to characterize the PA membranes, contact angle measurements and thermogravimetric analysis (TGA) were applied. It is shown that the presence of a residual organic solvent significantly changes the sorption and transport characteristics of the membranes. The residual organic solvent increases the amount of water absorbed by the polymer membrane. In pervaporation of water/ethyl acetate mixtures, the presence of the residual solvent dimethylacetamide makes the membrane more permeable but less selective for water separation.