The reaction of picryl benzoate derivatives 1a–g with aniline in methanol proceeds through COO and ArO bond cleavage pathways. Furthermore, the reactivity of these esters toward anilinolysis is correlated to the energy gap between highest occupied molecular orbital aniline and lowest unoccupied molecular orbital of each ester. The regioselectivity of acyloxygen versus aryloxygen cleavage is also discussed. The overall rate constants ktot split into kCOO (the rate constant of acyl-oxygen cleavage) and kArO (rate constant of aryl-oxygen cleavage). The COO bond cleavage advances through a stepwise mechanism in which the formation of the tetrahedral intermediate is the rate-determining step. The ArO bond cleavage continues through a SNAr mechanism in which the departure of the leaving group from the Meisenheimer complex occurs rapidly after its formation in the rate-determining step.