Cu-catalyzed reactions ofN-alkoxy-2-methylanilines and alcohols in the presence of catalytic amounts of IPrCuBr and AgSbF6afforded the correspondingmeta-aminophenol derivatives in good to high yields. These reactions proceed via a [1,3]-rearrangement, in which the alkoxy group migrates from the nitrogen atom to the methyl-substituted ortho position, followed by an oxa-Michael reaction of the resultingortho-quinol imine intermediate.