Thianthrene cation radical perchlorate ($Th^{+{{cdot}}}{ClO_4}^-$) reacted readily with two isomeric thiols, benzylthiol (1) and 4-methylbenzenethiol (7) in an acetonitrile solution at room temperature. From the reaction of 1, the major products, N-benzylacetamide (4) and benzyl sulfide (5), are characteristic of benzyl carbocations while the minor one, benzyl disulfide (6) implies free radical component of the reaction. It is unprecedented that the formation of a benzyl carbocation was caused by the extrusion of sulfur atoms from benzyl sulfur cations (3). In contrast, from the reaction of 7, only p-tolyl disulfide (10) was obtained from both sulfur radicals and cations. In the reaction of 7 the thio-extrusion was not observed from the p-tolyl sulfur cation (9). A thianthrene cation radical ($Th^{+{{cdot}}}$) was reduced quantitatively to thianthrene (Th) in both reactions.