The conformational dependence of the nuclear spin–spin coupling from methyl protons to ring protons, to the fluorine nucleus, and to protons of other methyl groups in toluene,p-fluorotoluene, and the xylenes is computed by the finite perturbation technique in the INDO approximation of molecular orbital theory. The calculated coupling over six bonds to the proton in the para position agrees quantitatively with experiment and its predicted dependence on the rotational angle of the methyl group supports a commonly assumed π electron mechanism for the transmission of spin information between the nuclei. Similar remarks apply to the fluorine nucleus inp-fluorotoluene. The couplings over five and four bonds to the protons in the meta and ortho positions display a more complex angular dependence and the former can be interpreted in terms of a dominant σ electron mechanism. The coupling between protons in different methyl groups in the ortho and meta xylenes is calculated as rather larger than the values observed in their derivatives and in the main shows the behavior expected from a π electron mechanism. Those conformations of ortho xylene in which the coupled protons are in close proximity yield computed values plausibly attributable to "direct" and/or "through-space" mechanisms. The preferred conformation of the methyl group in toluene is predicted to have a C—H bond eclipsing the plane of the aromatic ring and the calculated barriers to rotation of 0.013 kcal/mol in toluene and of 0.014 kcal/mol inp-fluorotoluene are in quantitative accord with microwave data.