Selenite reacts with S2O 32− forming SeS4O 62− and S4O 62− . When the stoichiometric ratio (1∶4) is changed, secondary reactions take place and precipitation, of selenium is observed. Excessive S2O 32− reacts with SeS4O 62− in neutral solutions forming SeSSO 32− , which decomposes to Se. In acidic solutions this reaction has a minor importance and causes a small Se-precipitation. The main product gives a build-up reaction, forming SeS5O 62− . Excessive SeO 32− also gives SeSSO 32− and SeS5O 62− . SeSSO 32− is decomposed by sulfite, forming SeSO 32− and S2O 32− . Thiosulfate reduces SeO 32− to SeS4O 62− . SeSO 32− gives, a build-up reaction with SeS5O 62− , forming Se2S5O 62− and Se3S5O 62− . Decomposition of Se3S5O 62− causes precipitation of a S/Se-mixture. SeSSO 32− , SeS5O 62− , Se2S5O 62− and Se3S5O 62− have been detected for the first time.