The present research is devoted to the synthesis and investigation of properties and structure of Ba-, Mn-, S-, and P- substituted Bi26Mo10O69. The complex oxides have been synthesized using conventional method. The samples were examined using XRPD, IR FT spectroscopy, Rietveld full profile structure refinement, SEM, laser diffraction, and densitometry. Photocatalytic properties were investigated at RhB oxidation under UV irradiation. Electrical conductivity was studied with impedance spectroscopy. As a result, the best samples of Ba-, Mn-, S-, and P- substituted Bi26Mo10O69 can be recommended as high ionic conductive materials.