2,2'-Bipyridyls have been utilized as indispensable ligands in metal-catalyzed reactions.T he most streamlined approach for the synthesis of 2,2'-bipyridyls is the dehydrogenative dimerization of unfunctionalized pyridine.H erein, we report on the palladium-catalyzed dehydrogenative synthesis of 2,2'-bipyridyl derivatives.The Pd catalysis effectively works with an Ag I salt as the oxidant in the presence of pivalic acid. A variety of pyridines regioselectively react at the C2-positions. This dimerization method is applicable for challenging substrates such as sterically hindered 3-substituted pyridines, where the pyridines regioselectively react at the C2-position. This reaction enables the concise synthesis of twisted 3,3'disubstituted-2,2'-bipyridyls as an underdeveloped class of ligands.