The design and synthesis of highly stable metal–organic frameworks (MOFs) bearing unpredictable polynuclear clusters and new topologies are important for the development of novel and complicated MOFs. Herein, the polynuclear rare-earth (RE) clusters with more coordination modes and the small V-shaped ligand (2,5-thiophenedicarboxylic acid) were chosen, and subsequently JLU-MOF132 with three different yttrium clusters (two independent Y6 and one Y9 clusters) and a novel (12, 12, 18)-connected topology was successfully synthesized. Notably, JLU-MOF132 exhibits high porosity, excellent thermal, acid-base, and solvent stabilities. JLU-MOF132 shows considerable potential in methanol-to-olefins (MTO) products (C3H6 and C2H4) separation. The high ideal adsorbed solution theory C3H6/C2H4 selectivities (9.2, 10.6, and 15.1) and the breakthrough experiments results, including the high C2H4 purity (>99.9 %) and productivities (26.1, 73.1, and 101.0 L·kg-1), demonstrate its practical purification capability. Semi-empirical tight binding (xTB) quantum chemical calculations explain the mechanisms that differentiate C2H4 and C3H6 adsorption in JLU-MOF132. In addition, JLU-MOF132 also displays outstanding radioactive iodine adsorption performance, with an iodine uptake of 750 mg·g-1 in vapor and 153 mg·g-1 in cyclohexane solutions. Briefly, this work not only demonstrates the viability of employing the V-shaped ligand to increase the structural diversity of highly stable MOFs, but also enhances the application potential of MOFs in the fields of the MTO products separation and radioactive iodine adsorption.