Through regulating the reaction solvent and temperature, two Tb-based metal–organic frameworks, ((CH₃)₂NH₂)₂[Tb₉(μ₃-OH)₈(μ₂-OH)₃(PTB)₆]·(DMF)₁₄·(H₂O)₁₉ (1) and ((CH₃)₂NH₂)₃{[Tb₉(μ₃-O)₂(μ₃-OH)₁₂(H₂O)₆][Tb₃(μ₃-O)(HCO₂)₃ (PTB)₆]}·(DMF)₁₂·(H₂O)₇ (2) (H₃PTB = pyridine-2,4,6-tribenzoic acid), have been synthesized. Structural analysis showed that the cluster node of 1 is a Tb₉ cluster, while 2 contains two different nodes of a Tb₃ cluster and a Tb₉ cluster, which leads to their different pore structures and may potentially separate C₂H₂/CO₂. Gas adsorption demonstrates that both MOFs can separate C₂H₂ and CO₂, but 2 has a more optimized pore environment than 1 and can exhibit better selective separation of C₂H₂/CO₂.