A new method for the Cu(OAc)(2)-catalyzed phenylation of tertiary alcohols under mild basic conditions is described. Triphenylbismuth(V) diacetate and tetraphenylbismuth reagents undergo cross-coupling reactions with alpha-hydroxycarbonyl compouds efficiently. For non-chelating tertiary alcohols, tetraphenylbismuth fluoride is found suitable as a phenyl donor.