In this article the possibility of synthesis of phases on the basis of Ba 4Ca 2Nb 2O 11 by heterovalent replacement F - → O 2- is studied. It is established that the samples Ba 4Ca 2Nb 2O 11-0,5xF x are single-phase in the range of 0 ≤ x ≤ 0.4 and are characterized by cubic structure of double perovskite. It is proved these phases are capable to dissociation water incorporation in structure from gas phase and high-temperature protonic conductivity. The conductivity of fluorine-doping samples was higher then undoped for 0.5 0.8 order of magnitude in region Т < 600 °С. Fluorine-doping method may be recommended as a general way for optimizing transport properties of oxygen and protonic conductors.