Abstract Redox properties of layer type chalcogenides of main group V elements were investigated in molten salt and organic Li+-electrolytes. Even at room temperature, Bi2S3, Bi2Se3 and Bi2Te3 can be reduced with about 100% material efficiency to Li3Bi as final product. The reduction of Bi2S3 to Bi0 and Li2S can be reversed in organic electrolytes.