The method of complete neglect of differential overlap was used to calculate the electronic structure of α PbF₂, β PbF₂, and PbCl₂ crystals which form the basic matrices for the synthesis of new superionic conductors. It was shown that the electronic subsystem is fairly stable on transition from the high-symmetry β PbF₂ crystal to the low-symmetry α PbF₂. The electronic structure of the cotunnite crystal PbCl₂ was calculated for the first time.