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An efficient synthesis of 5,7-dihydroxy-4-methylcoumarin from phloroglucinol with ethyl acetoacetate in the UiO-66-SO 3 H metal-organic framework is reported. The potential of UiO-66-SO 3 H as a solid catalyst was determined through optimized-condition experiments and quantum molecular calculations. The optimal conditions for the synthesis of 5,7-dihydroxy-4-methylcoumarin with UiO-66-SO 3 H were as follows: phloroglucinol/ethyl acetoacetate molar ratio = 1:1.6, reaction time = 4 h, and temperature = 140 °C, for which the reaction yield reached 66.0%. The reusability of UiO-66-SO 3 H catalysts for Pechmann condensation was examined. The activation energy of the reaction occurring on a sulfonic group of the UiO-66-SO 3 H catalyst was 12.6 kcal/mol, which was significantly lower than 22.6 kcal/mol of the same reaction on the UiO-66 catalyst. To comprehend the reaction mechanism, density functional theory with the ONIOM approach was applied for the synthesis of coumarin on the UiO-66-SO 3 H and UiO-66 clusters. A possible reaction mechanism was proposed involving three steps: a trans-esterification step, an intramolecular hydroxyalkylation step, and a dehydration step. The rate-determining step was suggested to be the first step which acquired an activation energy of 15.7 and 29.5 kcal/mol, respectively. Information from this study can be used as guidelines to develop more efficient catalytic metal-organic frameworks for various organic syntheses., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)