The liquid + liquid phase equilibrium of molten mixtures of lithium fluoride with potassium and rubidium halides was investigated over an extended temperature range in the two-phase region along the saturation line by the electrical conductivity method. In the overwhelming majority of mixtures, the electrical conductivity for coexisting equilibrium phases increased when the temperature increased. For mixtures with only potassium bromide, it decreased because of the extensive solubility of potassium bromide in lithium fluoride. The electrical conductivity for the light phase was half the value of the conductivity of the pure lithium fluoride. The electrical conductivity of the heavy phase did not differ enough from the conductivity of the pure heavy alkali halides. At the same time, the solubility of the heavy component in LiF was many times less than the lithium fluoride solubility in the lower phase. This contradiction points to essential reorganisation of the structure of the light phase. The difference between the conductivities of the coexisting phases at equal temperatures increased as the radius of the halide anion or alkali cation grew. The temperature growth led to the increase in the conductivity difference along the saturation line for mixtures of LiF with RbI. For mixtures of LiF with lighter alkali halides, it decreased up to zero at the critical mixing point for LiF + KBr mixtures as the temperature increased. Between the coexisting equilibrium phases, a transient layer was revealed, where a conductivity gradient exists. The thickness of this layer decreased as the temperature decreased and the sum of the ionic radii of the mixtures increased. (C) 2012 Elsevier Ltd. All rights reserved.