The kinetics of oxygenation of several para-substituted phenyl methyl sulfides and sulfoxides with a series of 5-substituted and sterically hindered oxo(salen)chromium(V) complexes have been studied by a spectrophotometric technique. Though the reaction of sulfides follows simple second-order kinetics, sulfoxides bind strongly with the metal center of the oxidant and the oxygen atom is transferred from the oxidant-sulfoxide adduct to the substrate. The reduction potentials, E(red), of eight Cr(V) complexes correlate well with the Hammett sigma constants, and the reactivity of the metal complexes is in accordance with the E(red) values. The metal complexes carrying bulky tert-butyl groups entail steric effects. Organic sulfides follow a simple electrophilic oxidation mechanism, and the nonligated sulfoxides undergo electrophilic oxidation to sulfones using the oxidant-sulfoxide adduct as the oxidant. Sulfoxides catalyze the Cr(V)-salen complexes' oxygenation of organic sulfides, and the catalytic activity of sulfoxides is comparable to pyridine N-oxide and triphenylphosphine oxide. The rate constants obtained for the oxidation of sulfides and sulfoxides clearly indicate the operation of a pronounced electronic and steric effect in the oxygenation reaction with oxo(salen)chromium(V) complexes.