We examined the challenge of preparing CO2-selective bifunctional three-dimensional Cu-metal-organic frameworks (Cu-MOFs) for use in mixed-matrix membranes (MMMs) fabricated on an asymmetric polymer support. Two different gas-selective micro-sized frameworks, [{Cu-2(Glu)(2)(mu-bPa)}center dot(CH3CN)](n) (Cu-MOF1) and [{Cu-2(Glu)(2)(mu-bPP)}center dot(C3H6O)](n) (Cu-MOF2) (Glu = glutarate, bpa=1,2-bis(4-pyridyl) ethane, bpp=1,3-bis(4-pyridyl)propane), were synthesised and dispersed in polyoxazoline (POZ), as a matrix for the fabrication of the MMMs. SEM imaging indicated relatively good adhesion between the Cu-MOFs and POZ, without any surface treatment. The ideal selectivity of CO2/N-2 was enhanced significantly in the Cu-MOF/POZ MMM, compared to that in a pristine POZ asymmetric membrane. Improvement in the CO2/N-2 selectivity of the membranes was achieved via both high adsorption selectivity of CO2 over N-2 by the Cu-MOFs, and the difference in pore sizes. The fabrication methods that use gas-selective MOFs may create new opportunities for gas-selective MOF/polymer combinations for MMMs with useful properties for large volume separations. (C) 2014 Elsevier B.V. All rights reserved.