The direct C–H arylation and acylation of azoles with carboxylic acids were achieved through Pd/Cu cooperative catalysis. Various biaryls and biaryl ketones were selectively produced in good to high yields from the same substrates. The key factor of high chemoselectivity was the choice of a suitable phosphine ligand: biaryls were generated selectively with dppp as the ligand, while biaryl ketones were obtained with high selectivity using dpph or Ph₂PCy as the ligand.