In the design and construction of porous materials, these with exceptional structure and composition are often highly expected, as they may offer unique nanopore space for desired applications. Here, a new family of quasi-3D and a 3D porous coordination polymers (PCPs) (termed NTU-43 to NTU-50) were constructed via an evolution strategy from a layered structure (termed NTU-42). Single gas adsorption isotherms of CO2, N-2, and CH4 display the dependency of gas capacity on optimized effects of pore size, functionality, and charged framework of these quasi-3D PCPs, where NTU-45 and NTU-46, the two with NH2-BDC and OH-BDC bidentate linkers (NH2-BDC = 2-aminoterephthalic acid and OH-BDC = 2-hydroxyterephthalic acid) have demonstrated outstanding ability for selective CO2 uptake. To the best of our knowledge, this is the first time to well explore the synergistic effects toward gas adsorption on a platform of quasi-3D frameworks. More importantly, the efficient CO2 capture from CO2/CH4 and CO2/N-2 mixtures has been also validated by breakthrough experiments under continuous and dynamic conditions at 298 K.