Benzyl trichloromethanesulfinates are easily obtained by oxidation of the corresponding sulfenates, in excellent yields. Examination of their reactivity revealed some unique features. In contrast to benzyl arenesulfinates which undergo solvolysis with complete S-O bond fission, these esters undergo solvolysis with exclusive C-O bond fission, and with a rate enhancement by a factor of 6 powers of ten, comparable to benzyl tosylates. Similarly, unlike benzyl arenesulfinates, these esters undergo a facile rearrangement to sufones ones on heating in polar nonhydroxylic solvents. A kinetic study of these reactions under various conditions has been performed, and the sensitivity of solvolysis to substituent and solvent effects has been analyzed by examination of the Hammett and Winstein correlations. The mechanisms of both reactions are discussed.