This study reports the fabrication of a highly hydrogen selective cross-linked polymer skin on a highly permeable mixed matrix membrane. Selective polymer skins were prepared by spin coating a thin layer of 6FDA-durene polymer onto ZIF-8/6FDA-durene mixed matrix membranes followed by subsequent cross-linking of the 6FDA-durene layer with ethylene diamine (EDA) vapor. Resultant membrane yielded significantly high gas pair selectivities for the separation of H-2/CO2, H-2/N-2 and H-2/CH4 of 29, 341, and 278, respectively, while also maintaining a high hydrogen permeability of 500 Barters. The superior separation performances of this system surpass the current permeability-selectivity tradeoff limits (Robeson 2008 upper bound) for H-2/CO2, H-2/N-2, and H-2/CH4 separations. The present work elucidates the potential of fabricating a highly selective layer (thin skin) on a highly permeable membrane to obtain high permeability and high selectivity simultaneously. (C) 2014 Elsevier B.V. All rights reserved.