Direct access to O-heterocycles by Bi(OTf)3-catalyzed intermolecular cyclization of phenols with diols is described. Catalytic dehydrative C–O and C–C bond tandem formations were achieved using a Bi(OTf)3 catalyst without any additives. The catalytic intermolecular cyclization of phenols with various diols proceeded to give the corresponding chromane (up to 91%) and/or pyran derivatives (up to 66%).