Tin oxide (SnO2) dissolves in cryolite-alumina melts forming tetravalent tin species, but under reducing conditions it is reduced to divalent tin and, further, to metallic tin. Freezing point depression data for SnF2 and SnO in molten cryolite (Na3AlF6) corresponded to the formation of one and two new particles, respectively. By anodic dissolution of tin into cryolite-alumina melts divalent as well as tetravalent tin was formed, depending on current density and composition. During electrolysis of SnO2-based oxygen-evolving anodes, the condensate above the melt contained both divalent (SnF2) and tetravalent (SnO2) tin species.