Metal oxide-supported palladium hydroxide (Pd(OH)2/MOx) catalysts enabled the oxidative intramolecular couplings of diarylamines to carbazoles and diarylethers to dibenzofurans via double aryl C-H bond functionalizations with molecular oxygen as the sole oxidant. While supported PdO, Pd, and palladium acetate catalysts showed poor catalytic activities, supported Pd(OH)2 exhibited remarkably high catalytic activity. Among supported Pd(OH)2 catalysts, Pd(OH)2/ZrO2 was found to be an efficient catalyst in terms of catalytic activities and selectivities for the synthesis of carbazoles and dibenzofurans.