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.