The reaction of 5,6-dithiabicyclo[2.1.1]hexane derivatives with OXONE in a two-phase mixture of dichloromethane and water gave the corresponding dithiirane derivatives which were stable in solution. The formation of the dithiiranes were proved by UV-Vis spectra and chemical transformations. The reaction of 7,8-dithiabicyclo[4.1.1]octane derivatives with OXONE gave the corresponding cis-dithiirane oxides. The reaction of the head-to-tail dimer of 2-adamantanethione with OXONE gave 2-adamantanone as the sole detectable material.