2, x-Dihalopyridines reacted with phenols catalyzed by CuI/TMEDA in the presence of Cs2CO3 in DMSO at 110° C under nitrogen atmosphere for 24 h to afford 2-aryloxypyridines in good to high yields except p-nitrophenol. To expand this methodology, a vanilloid receptor ligand used in treatments was prepared in good yield. This method has potential utility in the synthesis of pharmaceuticals, agrochemicals and even natural products.