This article demonstrates the successful fabrication of thin-film-composite (TFC) membranes containing well-defined soft-hard-soft triblock copolymers. Based on “hard” polyimide (PI) and “soft” polydimethylsiloxane (PDMS), these triblock copolymers (PDMS-b-PI-b-PDMS), were prepared via condensation polymerization, and end-group allylic functionalization to prepare the polyimide component and subsequent “click” coupling with the soft azido functionalized PDMS component. The selective layer consisted of pure PDMS-b-PI-b-PDMS copolymers which were cast onto a precast crosslinked-PDMS gutter layer which in turn was cast onto a porous polyacrylonitrile coated substrate. The TFC membranes' gas transport properties, primarily for the separation of carbon dioxide (CO2) from nitrogen (N2), were determined at 35 °C and at a feed pressure of 2 atm. The TFC membranes showed improvements in gas permselectivity with increasing PDMS weight fraction. These results demonstrate the ability for glassy, hard polymer components to be coated onto otherwise incompatible surfaces of highly permeable soft TFC substrates through covalent coupling. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014