The molecular structure of methyl trifluoromethanesulfonate (CH3OSO2CF3, methyl triflate) was investigated by gas electron diffraction (GED) and quantumchemical calculations (HF/3-21G* and B3LYP/6-31G*). The GED analysis revealed a gauche conformation (methyl group gauche with respect to CF3 group) with a dihedral angle phi(C-O-S-C) 89(7)degrees. This value is reproduced correctly by the calculations. Some calculated bond lengths and bond angles, however, differ from experimental values by up to +/-0.07 Angstrom and +/-6 degrees. Additional B3LYP/6-31G* calculations have been performed for some covalent sulfonates. The potential functions for internal rotation around the S-O single bond in FOSO2F and ClOSO2F possess minima for gauche and trans orientation of the O-X (X = F or Cl) bond. The trans minima are 1.6 and 1.3 kcal mol(-1) higher in energy. The potential functions for triflic acid, HOSO2CF3, for CH3OSO2Cl and CH3OSO2F possess minima only for gauche structures and maxima for trans orientation. These results are in partial contrast to previous experimental studies.