A copper-mediated dehydrogenative C-H/C-H biaryl coupling of phenols and 1,3-azoles has been developed. The key to its success is the introduction of a bipyridine-type bidentate auxiliary, 4,4'-di(tert-butyl)-2,2'-bipyridine, on the phenol oxygen, which is readily prepared and easily attachable, detachable, and recyclable. The reaction proceeds smoothly in the presence of copper salt alone to form the corresponding phenol-azole heterobiaryls, which are prevalent motifs in functional molecules such as excited-state intramolecular proton transfer materials.