3-Hydroxy-2-(trialkylsilyl)phenyl triflates are presented as new versatile hydroxyaryne precursors. These are base-activated aryne precursors induced via a C-sp-to-O 1,3-Brook rearrangement. The reaction of various arynophiles and 3-trialkylsiloxybenzyne generated from 3-hydroxy-2-(trialkylsilyl)phenyl triflate efficiently afforded highly regioselective phenol derivatives. Furthermore, through crossover experiments, the intramolecular mechanism of silyl migration was demonstrated.