Sulfoxide ligation to Pd(II) salts is shown to selectively promote C-H oxidation versus Wacker oxidation chemistry and to control the regioselectivity in the C-H oxidation products. A catalytic method for the direct C-H oxidation of monosubstituted olefins to linear (E)-allylic acetates in high regio- and stereoselectivities and preparatively useful yields is described. The method using benzoquinone as the stoichiometric oxidant and 10 mol % of Pd(OAc)2 or Pd(O2CCF3)2 as the catalyst in a DMSO/AcOH (1:1) solution was found to be compatible with a wide range of functionality (e.g., amides, carbamates, esters, and ethers, see Table 2). Addition of DMSO was found to be critical for promoting the C-H oxidation pathway, with AcOH alone or in combination with a diverse range of dielectric media, leading to mixtures favoring Wacker-type oxidation products (Tables 1, S3). To explore the role of DMSO as a ligand, the bis-sulfoxide Pd(OAc)2 complex 1 was formed and found to be an effective C-H oxidation catalyst in the absence of DMSO (eqs 2, 3). Moreover, catalyst 1 effects a reversal of regioselectivity, favoring the formation of branched allylic acetates.