Metal-free halogen(I) catalysts were used for the selective oxidation of aryl(heteroaryl)methanes [C(sp3)−H] to ketones [C(sp2)=O] or esters [C(sp3)−O]. The synthesis of ketones was performed with a catalytic amount of NBS in DMSO solvent. Experimental studies and density functional theory (DFT) calculations supported the formation of halogen bonding (XB) between the heteroarene and N-bromosuccinimide, which enabled imine–enamine tautomerism of the substrates. No additional activator was required for this crucial step. Isotope-labeling and other supporting experiments suggested that a Kornblum-type oxidation with DMSO and aerobic oxygenation with molecular oxygen took place simultaneously. A background XB-assisted electron transfer between the heteroarenes and halogen(I) catalysts was responsible for the formation of heterobenzylic radicals and, thus, the aerobic oxygenation. For selective acyloxylation (ester formation), a catalytic amount of iodine was employed with tert-butyl hydroperoxide in aliphatic carboxylic acid solvent. Several control reactions, spectroscopic studies, and Time-Dependent Density Functional Theory (TD–DFT) calculations established the presence of acetyl hypoiodite as an active halogen(I) species in the acetoxylation process. With the help of a selectivity study, for the first time we report that the strength of the XB interaction and the frontier orbital mixing between the substrates and acyl hypoiodites determined the extent of the background electron-transfer process and, thus, the selectivity of the reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim