An efficient and highly regioselective palladium-catalyzed ortho-C(sp(2))-H bond alkoxylation of 2-aryloxypyridines was developed using 2-pyridyloxyl as the directing group and alcohols as alkoxylation reagents. Under an air atmosphere and in the presence of PhI(OAc)2, the reaction gave the corresponding products in moderate to good yields, and a series of functional groups could be tolerated.