Metalloporphyrins are present naturally in cytochromes and hemoglobins. Perhaps the most interesting feature of heme-enzymes, such as cytochromes P450, is their ability to perform extremely difficult oxidations with high selectivity. The present work is undertaken with the aspiration of designing the mechanistic studies on meso-tetraphenylporphyriniron(III) chloride catalyzed oxidation of anilines by potassium peroxymonosulfate (oxone) in aqueous acetic acid medium. The study of oxidation with respect to the catalyst reveals that there is degradation of the catalyst. The concentration-protonated aniline (a less reactive species) increases due to the increase in [H+], which inhibits the rate of the reaction. The thermodynamic parameters for the oxidation have been determined and discussed. It confirms the Exner relationship and also the activation parameters to the isokinetic relationships. The oxone oxidation with 12 meta- and para-substituted anilines complies with the isokinetic relationship but not with any of the linear free energy relationships. The solvent interaction plays a major role in governing the reactivity. A suitable mechanism is proposed for this reaction.