<p>Comprehending how substituent effect influences catalytic performance is essential for advancing efficient catalysts and unraveling reaction mechanisms. Examining the substituent effects of metal corrole catalyzed Baeyer–Villiger (B–V) oxidation reaction remains limited. In this work, four iron tri-aryl corrole complexes with distinct electronic structures, iron(IV) 5,10,15-tris(pentafluorophenyl) corrole [Fe^IV(TPFC)Cl] (<b>1</b>a), iron(IV) 5,15-bis(pentafluorophenyl)-10-phenyl corrole [Fe^IV(BPFPC)Cl] (<b>2</b>a), iron(IV) 5,15-bis(phenyl)-10-pentafluorophenyl corrole [Fe^IV(BPPFC)Cl] (<b>3</b>a) and iron(IV) 5,10,15-tris(phenyl) corrole [Fe^IV(TPC)Cl] (<b>4</b>a) have been prepared. The impact of electron-withdrawing meso-substituents on their catalytic performance in B-V oxidation reaction was then investigated. The results reveal that an increased number of pentafluorophenyl substituents, which enhance the electron-withdrawing effect, correlates with superior catalytic activity. The catalytic activity follows an order <b>1</b>a &gt; <b>2</b>a &gt; <b>3</b>a &gt; <b>4</b>a. The plausible mechanism to explain the observed catalytic behavior was also discussed.</p> Graphical Abstract <p></p>