Optical resolution of (1RS, 3SR)-(1) and (1RS, 3RS)-(2) dithiirane 1-oxides was achieved by HPLC equipped with a chiral column to give 1a and 1b and 2a and 2b, respectively. X-ray analyses proved absolute configurations of 1a and 1b to be (1R, 3S) and (1S, 3R), while those of 2a and 2b were determined to be (1R, 3R) and (1S, 3S), respectively, since 2a and 2b isomerized stereospecifically to 1b and 1a, respectively. Enantiomeric dithiirane 1-oxides 1a and 1b reacemized to each other whereas 2a and 2b did not. To the racemization (oxygen migration) is proposed a mechanism involving homolysis of the S(O) S bond at the initial step followed by a ring closure giving a 1,2,4-oxathietane intermediate. Isomerization between 1 and 2 was inhibited by a radical scavenger, DPPH.