An efficient route to 4-aryl-2-naphthols from arynes and aroylacetones was developed by carbon–carbon bond insertion followed by an intramolecular aldol reaction and dehydration. Benzyne derived from 2-(trimethylsilyl)phenyl triflate reacted with benzoylacetones in refluxing acetonitrile to give 4-aryl-2-naphthols and 3-aryl-1-naphthols.