In this paper we show the possibility of oxyanion doping in complex oxides with disordered oxygen vacancies. The homogeneity region of solid solutions Ba 4Ca 2Nb 2-xP xO 11 is x=0.0-0.5. The temperature dependencies of conductivity are investigated. It is demonstrated that the introduction of small amounts of phosphorus increases the total conductivity of the system Ba 4Ca 2Nb 2-xP xO 11, besides the introduction of phosphorus increases the temperature of system’s response to humidity up to 800 ° C.