Membrane methods are environmentally friendly and can significantly improve the design and development of new energy consumption processes that are very important nowadays. However, their effective use requires advanced membrane materials. This study aims to improve the performance of pervaporation polyvinyl alcohol (PVA)-based membrane for isopropanol dehydration. To achieve this goal, two methods were applied: (1) bulk modification of PVA by Pluronic F127 and (2) development of supported PVA-based membrane using polyphenylene isophthalamide (PA) as a substrate with a various porosity. Developed membranes were characterized by Fourier-transform infrared spectroscopy, scanning electron microscopy (SEM), contact angle measurement, and swelling experiments. The concentration influence of PA casting solution (12–20 wt.%) on the performance of porous PA membranes (substrates) was investigated in ultrafiltration of pure water and bovine serum albumin (BSA) solution as well as by microscopic methods (SEM and atomic force microscopy). The developed dense and supported PVA-based membranes were tested in the pervaporation dehydration of isopropanol. Optimal transport characteristics were obtained for a supported membrane with a PVA-based selective layer containing 3 wt.% Pluronic F127 onto an ultrafiltration PA (17 wt.%) substrate: improved permeation flux 0.100–1.164 kg/(m² h) and 98.8–84.6 wt.% water content in the permeate in pervaporation dehydration of isopropanol (12–80 wt.% water).