Persulfate-mediated decarboxylation of arylacetic acids is well-versed and a preferred choice for functionalization. However, certain substituted arylacetic acids do not follow the expected decarboxylation trend and may lead to other different functionalizations, which remain elusive in the literature. The effect of ortho-substitution on persulfate-mediated decarboxylation and functionalization of arylacetic acids forms the basis of this report, wherein the presence of different electron-withdrawing or electron-releasing groups exerts different effects on the fate as well as rate of decarboxylation. In so doing, the synthesis of ortho-hydroxy N-arylacetamides under persulfate-mediated one-pot conditions is developed.