Voltammetry is applied to study Sn(0)/Sn(II) and Sn(II)/Sn(IV) equilibria in CR 1.8 cryolite melt with 2 wt.% alumina. Formal potentials of redox processes on platinum, carbon and tin dioxide anodes are determined for various SnO concentrations. These data are used to construct an approximate scale of potentials for redox transformations of various tin-based species. The resulting scale is compared to the values computed from currently available thermodynamic data, and the difference is considered as the estimate of solvation energy. Possibilities to control and monitor the processes in the bath with tin-containing low-consumable anodes on the basis of tin electrochemistry data are discussed.