This account presents palladium-complex-catalyzed oxidative couplings mainly developed by the author’s group, including oxidative amination and silylation of terminal alkenes, direct oxidative arylation of aromatic compounds, and oxidative difunctionalization of 1,3-dienes. The catalytic cycles in these representative reactions feature re-oxidation of the palladium species with molecular oxygen as the terminal oxidant. Varying the combination of palladium catalyst and re-oxidant enables the formation of a variety of bonds through dehydrogenative cross-coupling reactions.