We have examined the intermediacy of sulfur-centred radical cations in the one-electron oxidation of (anthracen-9-yl)methyl sulfides. Reaction of (anthracen-9-yl)methyl sulfides with ceric ammonium nitrate (CAN) gave predominantly nitration and oxidation products along with products arising through sulfur-centred radical cations in minor amounts. Upon irradiation, (anthracen-9-yl)methyl sulfides underwent efficient intramolecular single electron transfer leading to a variety of products arising through the intermediacy of sulfur-centred radical cations.