Regions of the formation of tetragonal solid solutions with the γ-LiAlO2 structure and the co-cation conduction are studied in the systems 0.9Na1-xLixAlO2-0.1EO2 (E = Ti, Ge, Si) and 0.8Na1-xLixAlO2-0.2TiO2. The single-phase regions of solid electrolytes narrows down with decreasing size of cations of a rigid lattice. No polyalkaline effect exists in the above systems. In the single-phase region of solid solutions, variations in the conductivity is caused largely by variations in the partial conductivity of the more mobile sodium cation.