The use of perovskite-type layered oxide K₂La₂Ti₃O₁₀ (Per) as a modifier of the Torlon® polyamide-imide (PAI) membrane has led to the formation of an specific structure of a dense nonsymmetrical film, namely, a thin perovskite-enriched layer (3-5 μm) combined with the polymer matrix (~30 μm). The PAI/Per membrane structure was studied by SEM in combination with energy dispersive microanalysis of the elemental composition which illustrated different compositions of top and bottom surfaces of the perovskite-containing membranes. Measurement of water and alcohol contact angles and calculation of surface tension revealed hydrophilization of the membrane surface enriched with perovskite. The transport properties of the nonsymmetrical PAI/Per membranes were studied in the pervaporation of ethanol-ethyl acetate mixture. The inclusion of 2 wt. % Per in the PAI gives a membrane with a high separation factor and increased total flux.