Development of novel membranes with optimal performance, selectivity, and stability is a key research area in membrane technology. In the present work aromatic polyamidoimideurea (PAIU) is synthesized and tested as promising membrane material for separation of water and alcohol mixtures. The PAIU membrane structure, density, and transport properties are studied. Mass transfer of water and isopropanol through the membrane is estimated by sorption and pervaporation tests to determine equilibrium sorption degree, diffusion coefficients, flux through the membrane, and separation factor. Two techniques of sorption study from liquid and from vapor phases are used as novel approach to experimental study of mass transfer. The vapor sorption calorimetry permits to analyze the behavior of the polymer material in sorption process. In pervaporation of water-isopropanol mixture, almost pure water mainly permeates through PAIU membrane. To improve the performance, a double layer membrane containing a thin PAIU layer on the surface of porous poly(phenylene oxide) support is developed. The double layer membrane is extremely effective in dehydration of isopropanol.