Alkyl alkanesulphonates and arenesulphonates were found to be useful sources of sulphonyl radicals, particularly for spectroscopic work, when treated with organotin or organosilyl radicals. Allyl, propynyl and penta-2,4-dienyl methanesulphonates gave, however, allyl, propynyl and pentadienyl radicals, respectively. Sulphonyl radicals generated in this way added efficiently to alk-1-enes with electron-releasing substituents, and the EPR spectra of the adduct radicals were recorded. A variety of radical initiation systems were tried on pent-4-enesulphonyl chloride. The pent-4-enesulphonyl radical cyclised mainly in the endo mode to give the six-membered-ring sulphone. Similarly, the hex-5-enesulphonyl radical cyclised to give thiepane 1,1-dioxide, with a seven-membered ring. The cyclohex-2-enylethanesulphonyl radical cyclised mainly in the exo mode to give 2-chloro-9-thiabicyclo[4.3.0]nonane 9,9-dioxide. The mechanisms of these reactions are discussed.