A controlled regioselective synthesis of either C-2 or C-3 substituted benzo[b]furans from readily accessible 1-(2-hydroxyphenyl)-2-chloroethanones is described. Addition of a range of Grignard reagents to the α-chloro ketones generates alkoxide intermediates, which can form either 2-substituted benzo[b]furans via a [1,2]-aryl migration or 3-substituted benzo[b]furans via a direct cyclization and dehydration sequence. A temperature-dependent [1,2]-aryl migration mechanism for the formation of 2-substituted benzo[b]furan is proposed.