The synthesis of highly porous frameworks has received continuous research interest, but achieving the ability to target stable and selective materials remains challenging. Herein, by utilizing a 'direction-oriented' strategy and modulating reaction conditions, two novel 3D porous supramolecular organic framework (SOF) materials ( and , as isomers) are assembled from a non-planar building block (TMBTI = 2,4,6-trimethyl benzene-1,3,5-triyl-isophthalic acid) and they display permanent porosity, high thermal stability, and good recyclability. It is worth mentioning that the CO uptake values of and rank among the highest values for SOF-based materials under ambient conditions. Furthermore, these two materials exhibit preferential adsorption of CO over N and CH, and can effectively separate the mixtures of light hydrocarbons. These studies indicate the possible application of and in trapping greenhouse gases and upgrading natural gas. In addition, this synthetic strategy introduces an effective method for developing remarkable 3D SOFs among other framework materials.