In conclusion, employing the isoreticular series of UZr-X as model systems, the UZr–NH₂ exhibits the highest activity, achieving a yield of 81% after 10 h of reaction. This performance surpasses that of aminomodified MTi-NH₂ and MIn-NH₂, which can be attributed to the optimal electronegativity of Zr⁴⁺. DRFTIR analyses confirmed the generation of activated CO₂^– species during the reaction. Concurrently, the formation of NH₂–CO₂ and N–CO₂ coordination models has been validated through theoretical calculations. Thus, in conclusion, the amino substituent and exposed zirconium sites are the crucial active sites for this reaction. In essence, the interplay between the Lewis acid/base active site and the adsorption-coordination effect culminates in the superior performance observed in CO₂ cycloaddition.