A series of S- and P- doped Bi26Mo10O69 was synthesized by conventional solid state method and studied. Chemical analysis detected closeness of experimental and theoretical ratios of bismuth, molybdenum and dopant for P-doped samples and 50% deficiency of sulfur for S-doped samples. The solid solutions ranges were determined to be x = 0-0.7 for Bi26MO10-2xP2xO69-d and x = 0-0.6 for Bi26Mo10-2xSxO69-d. Stabilization of the monoclinic form is observed when x > 0.1 for P and x > 0.4 for S doping. The IR FT spectroscopy and Rietveld whole profile structure refinement at X-Ray diffraction data showed substitution of Mo by S and P forming SO4 and PO4 groups. The geometrical sizes of particles were determined to be in the range of 1-20 mu m. Materials under study are characterized with total ionic conductivity of the 1 x 10(-4) - 9 x 10(-3) S cm(-1) at 273-1073 K.