A new and mild synthetic approach has been developed for the synthesis of pharmaceutically important unsymmetrical diarylpyridines via chemoselective Suzuki-Miyaura coupling reactions of bromo-2-sulfonyloxypyridines. Most reactions allow for facile access to aryl-2-sulfonyloxypyridines at room temperature in yields of 5-99% with excellent chemoselectivity in the presence of Pd(OAc)2 (2.0 mol %) and Ad2BnP (2.4 mol %). The second arylation of the remaining tosyl or triflyl group in the monoarylpyridine derivatives obtained was successfully accomplished for the synthesis of unsymmetrical 2,3-, 2,4-, 2,5-, and 2,6-diarylpyridine derivatives. Furthermore, a one-pot synthesis of unsymmetrical diarylpyridines starting from bromo-2-sulfonyloxypyridine was accomplished to demonstrate the practical convenience. Finally, with this method, an antibacterial agent, a topoisomerase inhibitor, and etoricoxib, a nonsteroidal anti-inflammatory drug, were successfully synthesized from the corresponding bromo-2-hydroxypyridines in overall yields of 80, 86, and 49%, respectively.