Two new porous coordination polymers (PCPs), ([Cu-6(L)(4)center dot(H2O)(6)]center dot 0DMA center dot 4EtOH, (1) and [Cu-5(L)(2) (OH)(2)center dot(H2O)(2)center dot DMA(2)]center dot 2DMA center dot EtOH center dot 2H(2)O (2), were solvothermally synthesized and structurally characterized. Interestingly, their variable architectures controlled by solvent system exhibit a structural progression from an unusual non-crystallographic (NC) net to a (4,6)-connected framework with fsh topology. Moreover, the combination of 3D channels of about 3.0 x 7.2, 4.7 x 9.5, and 6.3 x 7.8 angstrom(2), and functional -OH groups in 2' lead to good selectivity of CO2 over CH4 (26-55 by IAST) at 273 K.