Abstract: The addition of the hypervalent iodine reagent PIFA [phenyliodine(III) bis(trifluoroacetate)] to a series of styrene type compounds results in the bis(trifluoroacetoxylation) of the double bond as two possible 1,2- and 1,1-regioisomers. We found that 1,1-regioisomers resulted to be unstable during chromatographic purification yielding the related arylacetaldehydes. In this communication we show our efforts to explore the regioselectivity of this reaction, and to rationalize the results with respect to the electronic nature of the corresponding aryl ring through alternative mechanistic pathways.