The molecular orientation in self-assembled monolayers of ortho, meta, and para isomers of methyl-benzylmercaptans (OMBM, MMBM, and PMBM, respectively) on Au(111) has been studied using broad-bandwidth sum frequency generation spectroscopy and cyclic voltammetry. Cyclic voltammograms for the reductive desorption suggest that all methylbenzylmercaptans form closely packed monolayers. Sum frequency vibrational spectra for OMBM, MMBM, and PMBM show the CH3 symmetric stretching vibration mode. The vibrational intensities are greatest in PMBM and smallest in OMBM, implying the difference in the orientation of the methyl group. The vibrational intensities are compared with the hyperpolarizabilities of methylbenzylmercaptans from a calculation based on the density functional theory. OMBM molecules adsorb on Au(111) tilting their benzyl moieties so that the direction of the methyl group is parallel with the surface, whereas MMBM and PMBM molecules adsorb on Au(111) with their benzyl moieties being perpendicular to the surface.