The structures and the torsional potentials for the rotation around the aryl-SR bond of a series of neutral alkyl aryl sulfides and their corresponding radical cations were studied by applying density functional theory at the B3LYP/6-311G** level. In all radical cations the most stable conformer corresponds to the structure in which the S-alkyl group is in the planar conformation, with sulfur and alkyl atoms coplanar with the aromatic ring. The rotational energy barriers were relatively high, ranging from 12.307 to 19.496 kcal/mol. In all cases substantial geometrical changes with respect to the parent sulfide were observed, the radical cation presenting a quinoidic structure, with quasi-single bonds alternating to quasi-double bonds, and a shorter C-Ar-S bond. These results illustrate the importance, in the radical cation, of the conjugation between the sulfur atom and the aromatic pi system. Such a conjugation is not so important in the neutral molecules and in fact the energy minimum for alkyl phenyl sulfides is located in correspondence of the perpendicular form, with the exception of thioanisole for which the two effects seem to have a similar role. Calculation of Mulliken spin populations, MK and NPA charges showed that PhSR.+ and 4-NCC6H4SR.+ are mainly sulfur-centered radical cations, whereas 4-Me2NC6H4SMe.+ and 4-MeOC6H4SMe.+ are essentially aromatic radical cations with some charge and spin density at the sulfur atom. Ionization energies were also calculated for both the planar and perpendicular forms; for the PhSR series (particularly in the former case), they resulted in good agreement with the experimental ones.