Several compounds may exist in LnCl3–MCl mixtures. Those corresponding to the M2LnCl5 and MLn2Cl7 stoichiometries are formed in a few systems only, with diverse stability strongly dependent on both the corresponding lanthanide and alkali metal. On the other hand, M3LnCl6 that occur in most systems have a far larger stability range and melt congruently. These latter compounds were investigated in the present work by differential scanning calorimetry and electrical conductivity measurements. The thermodynamic and transport properties were correlated to structural features and related to the mechanism of compound formation.