A palladium-catalyzed direct sulfonylation of 2-aryloxypyridines on the ortho-position of the benzene ring was developed using 2-pyridyloxyl as the directing group and sulfonyl chlorides as sulfonylation reagents. The protocol was available for both electron-rich and electron-deficient substrates. The ortho-sulfonylated phenol was synthesized expediently from the sulfonylation product by the removal of the pyridyl group.