Lithium-containing bismuth titanates with the pyrochlore-type structure Bi1.6LixTi2O7–δ were obtained for the first time. The formation of the pyrochlore phase was confirmed by X-ray diffraction analysis, scanning electron microscopy and local microanalysis. In Bi1.6MxTi2O7–δ, the lithium and indium are occupied the bismuth sites, primarily. The electrophysical properties of doped bismuth titanates were studied by impedance spectroscopy in the frequency range 1–106 Hz. In the low-temperature range (of up to ~400°C), electron conductivity predominates; above 400°C, the oxygen-ion type of conductivity is revealed. In the range p(O2) = 0.21–1 atm, the average value of the sum of ion transport numbers is 0.5 at 500–550°C. The relaxation process was found from the frequency dependences of the dielectric parameters (ε', tan δ, M''), which was of the same type for systems with different dopants (In, Li) probably due to the hopping mechanism of oxygen conductivity.