Aryl-substituted epoxides and aliphatic epoxides with a tertiary epoxide carbon undergo smooth rearrangement in the presence of 10–50 mol% bismuth(III) oxide perchlorate, BiOClO4•xH2O, to give carbonyl compounds. The rearrangement is regioselective with aryl substituted epoxides and a single carbonyl compound arising from cleavage of benzylic C―O bond is formed. BiOClO4•xH2O is relatively non-toxic, insensitive to air and inexpensive, making this catalyst an attractive alternative to more corrosive and toxic Lewis acids such as BF3•Et2O or InCl3 currently used to effect epoxide rearrangements.