Several experimental techniques were used to characterise the physicochemical properties of the TbBr3-NaBr system. The phase diagram determined by DSC, exhibits an eutectic and a Na3TbBr6 stoichiometric compound that decomposes peritectically (759 K) shortly after a solid-solid phase transition (745 K). The eutectic composition, x(TbBr3)=39.5 mol%, was obtained from the Tamman method. This mixture melts at 699 K. With the corresponding enthalpy of about 16.1 kJ mol-1. Diffuse reflectance spectra of the pure components and their solid mixtures (after homogenisation in the liquid state) confirmed the existence of new phase exhibiting its own spectral characteristics, which may be possibly related to the formation of Na3TbBr6 in this system. Additionally, the electrical conductivity of TbBr3-NaBr liquid mixtures was measured down to temperatures below solidification over the whole composition range.