The alcohol permeability and permselectivity properties as well as the morphology of membranes made of a newly developed AB-cross-linked copolymer system composed of elastomeric and glassy components were investigated. The copolymer was synthesized by a hydrosilylation reaction between poly(styrene-stat-isoprenes) (Mn from 40,000 to 100,000 g/mol) with high content in unsaturated side groups (≈ 60% of entire isoprene content) and polyhydrogen polysiloxanes with varying SiH content (0.75 10.7 mol %) and molecular mass, Mn, from 2,500 to 36,000 g/mol. A two-track approach was taken to determine the morphology of the copolymer system. The first employed the usual polymer characterization methods such as electron microscopy, DSC, IR spectroscopy, the density gradient method, and mechanical measurements. For the second approach, different copolymer permeability models were tested so as to give an insight into the copolymer morphology. As a final step, the permeability and permselectivity properties were correlated with the morphological structure of the copolymer system. It was observed that the respective continuous microphase dominated the copolymer's physical properties, as, e.g., permeability, permselectivity, and mechanical properties. The microphase inversion in the copolymer system was proved by the permeability/permselectivity as well as by the mechanical measurements.