Catalytic systems RhCl3-KI-NaCl and RhCl3-Cu(OAcf)(2)-NaCl in aqueous perfluorinated carboxylic acids (CF3COOH, C3F7COOH) are effective in coupled oxidation of alkanes and carbon monoxide with dioxygen. In their presence, predominant is the outer-sphere oxidation of alkanes into respective esters (alcohols) with involvement of peroxo rhodium species as an oxidant (mechanism A). The process occurs partially by the inner-sphere mechanism B involving Rh-alkyl intermediates. Mechanism B is supported by (a) formation of alkyl chlorides, (b) synthesis of acetic acid in conversion of methane, and (c) positional selectivity in oxidation of propane. (C) 2016 Elsevier B.V. All rights reserved.