Irradiation of aryloxy-ketones ArO·CHR1·COR2(R1= H, alkyl, or Ph; R2= alkyl or Ph) in methanol caused fission of the C–OAr bond to give a phenol (ArOH), a ketone (R1CH2·COR2), and a product of ortho-rearrangement which cyclised during work-up to a substituted benzofuran. The benzofurans were also synthesised by cyclisation of suitable aryloxy-ketones in polyphosphoric or sulphuric acid. In a few cases, aryloxy-ketones gave the corresponding dimethyl acetals [ArO·CHR1·C(OMe)2R2] upon irradiation.