Quantum mechanics combined with thermostatistical computations allowed us to establish the binary lithium potassium halide melt dissociations. These latter can be well described taking into account the formation both of simple and complex ions LiX + 2KX reversible arrow Li+ + 2K(+) + 3X(-) [i] reversible arrow LiX(2) + K(2)X(+) [ii] Except for the lithium iodide-potassium iodide molten mixtures, whose dissociations are satisfactorily described assuming the formation of simple ions only (reaction i), the existence of the ionic complexes LiX(2)(-) and K(2)X(+) explains qualitatively the electrical conductivity of melts whatever the melt composition and temperature.