Metal-organic frameworks (MOFs) represent a kind of low-energy physisorbent with modifiable pores and framework structures; however, a deep understanding of how these structural features influence properties is a prerequisite for the rational design and development of tailor-made materials for advanced applications. In this report, a MOF, [Ni 2 (TCPP-Ni) 1/4 (TPIM) 2 (COOH)F][(Me 2 NH 2 )SiF 6 ]· xS (SDU-CP- 1 ; S = solvent molecules, SDU = Shandong University, and CP = coordination polymer), assembled by tetrakis(4-carboxyphenyl)porphyrin (TCPP-Ni) and 2,4,5-tris(4-pyridyl)imidazole (TPIM) ligands as well as Ni 2+ cations is reported. Interestingly, inorganic SiF 6 2- anions do not serve as the pillars like precedents in the framework but are just counterions, which endows SDU-CP- 1 with high uptake for C 2 H 2 and adsorption selectivity (2.5-4.2) for C 2 H 2 /CO 2 at room temperature, as certified by gas adsorption and separation experiments and grand canonical Monte Carlo calculation.