The electrical conduction in sintered fluorocomplexes LimMF6, MAl, Ti was investigated by electrochemical methods. New electrolytic cells were designed to check the charge carrier in such materials and the ionic transport numbers were measured. Fluorocomplexes examined here showed the lithium ion conduction; the conductivities were 2×10−4 and 6×10−5S cm−1 at 300°C for Li2TiF6 and Li3AlF6, respectively. Addition of different kinds of lithium fluorocomplex to introduce lattice defects (lithium ion vacancies or interstitial lithium ions) enhanced the electrical conductivity. A small electronic contribution to conduction was observed in Li2TiF6-based conductors.