Abstract: A method for producing biphenyl and its derivative comprising oxidatively coupling a benzene aromatic compound in the presence of a catalyst comprising a palladium salt, a copper salt, and a bidentate ligand compound capable of forming a complex with the palladium salt via the nitrogen atom and the oxygen atom in the molecule thereof in an atmosphere containing molecular oxygen. In particular, an improved method for selectively producing an asymmetrically substituted biphenyl derivative, such as a 2,3,3′,4′-biphenyltetracarboxylic acid tetraester, which comprises oxidatively coupling a substituted aromatic compound, such as a phthalic diester, in the presence of the catalyst in an atmosphere containing molecular oxygen without replenishing with a ligand.