Solvolyses of monomethoxy- and dimethoxyphenyl(phenyl)iodonium (ArI+Ph) tetrafluoroborates were carried out in methanol and 2,2,2-trifluoroethanol (TFE) at 130 °C. The solvolysis products include alkoxide substitution products (ArOR and PhOR) as well as iodoarenes (PhI and ArI). The ratios of ArOR/PhOR range from 8/2 to 4/6. The results are argued against formation of aryl cation. Copyright © 2007 John Wiley & Sons, Ltd.