C−H hydroxylation of aryl acetamides and alkyl phenylacetyl esters was accomplished via challenging distal weak O-coordination by versatile ruthenium(II/IV) catalysis. The ruthenium(II)-catalyzed C−H oxygenation of aryl acetamides proceeded through C−H activation, ruthenium(II/IV) oxidation and reductive elimination, thus providing step-economical access to valuable phenols. The p-cymene-ruthenium(II/IV) manifold was established by detailed experimental and DFT-computational studies. © 2020 The Authors. Published by Wiley-VCH GmbH