In this work, inspired by a water-assisted three-dimensional supramolecular structure 1, we use a mixed-ligand strategy to form a 3D pillared-layered matrix by the introduction of linear ligands to compete against the water molecules. The resulting analogue microporous MOFs of 2-H, 2-F and 2-N, decorated with different functional groups, similarly show the CO2 uptake. Thanks to the negligible N2 adsorption capacity, enhanced selective adsorption towards CO2 is achieved in compound 2-N. That is, we present here an alternative plan for the high CO2 selective adsorption performance. In addition, the structure stability and moderate affinity for CO2 of these microporous MOFs endow them with excellent reusability.