The conformational preferences and barriers to internal rotation about the S—C(phenyl) bond have been investigated for thioanisole and its 2-fluoro, 2,6- and 3,5-difluoro, and 2,3,5,6-tetrafluoro derivatives. Measurements of long-range spin–spin couplings between the methyl carbon and the para ring proton indicate that the 2-fluoro and 3,5-difluoro compounds prefer conformations with all heavy atoms coplanar. The 2,6-difluoro and 2,3,5,6-tetrafluoro compounds prefer conformations in which the methyl carbon lies in or near the plane perpendicular to the aromatic ring. Semiempirical molecular orbital calculations with the MNDO method indicate that all of the molecules prefer perpendicular conformations while similar calculations with AM1 indicate that all prefer planar conformations. Apparently the conformational behaviour can be quite sensitive to subtle changes in intramolecular interactions, which may indicate improvements to these semiempirical methods. The NMR results have been used to derive an internally consistent set of rotational potentials. Synthetic photoelectron spectra derived from these potentials and the AM1 orbital energies are in good agreement with the experimental spectra.