This paper describes the synthesis of unsymmetrical biaryls by the palladium-catalyzed cross-coupling reaction of acyl chlorides with potassium perfluorobenzoates. This transformation is unique in that it involves simultaneous decarbonylation and decarboxylation under redox-neutral conditions. Compared to conventional cross-coupling protocols for the synthesis of unsymmetrical biaryls, the two reactants in this synthetic strategy can be readily prepared from abundant and inexpensive aromatic carboxylic acids.