A mixture of molecular iodine and phenyliodine(III) bis(trifluoroacetate) (BTI) in CH 3 CN (or CH 3 OH) iodinates the aromatic ring of some activated alkyl aryl ketones. A different outcome results if PhSeSePh is used instead of I 2 in the presence of BTI. In CH 3 CN the aromatic phenylselenenylation is still observed while in CH 3 OH the formation of α-phenylseleno ketones occurs followed by the conversion of these intermediates into the corresponding α,α-dimethoxycarbonyl compounds, in moderate to good yields.