Tetratopic organic linkers have been extensively used in Zr-based metal–organic frameworks (MOFs) where diverse topologies have been observed. Achieving meticulous control over the topologies to tune the pore sizes and shapes of the resulting materials, however, remains a great challenge. Herein, by introducing substituents to the backbone of tetratopic linkers to affect the linker conformation, phase-pure Zr-MOFs with different topologies and porosity were successfully obtained under the same synthetic conditions. The conversion of CO₂ to valuable cyclic carbonates is a promising route for the mitigation of the greenhouse gas. Owing to the presence of substrate accessible Lewis acidic Zr(IV) sites in the 8-connected Zr₆ nodes, the Zr-MOFs in this study have been investigated as heterogenous acid catalysts for CO₂ cycloaddition to styrene oxide. The MOFs exhibited drastically different catalytic activities depending on their distinct pore structures. Compared to previously reported MOF materials, a superior catalytic activity was observed with the mesoporous NU-1008, giving an almost 100% conversion under mild conditions.