A glass-crystal composite (g-NCP/PCP), comprising a glassy nonporous coordination polymer (g-NCP) and a crystalline porous coordination polymer (PCP)/metal-organic framework, was synthesized by using a melt-quenched method. Compared to that of the PCP itself, g-NCP/PCP has an enhanced gas adsorption selectivity. The results should stimulate further studies of the chemistry of g-NCP/PCP glass-crystal composites.