The study of structural and electrical properties of three pure bismuth molybdate phases, α -Bi 2 Mo 3 O 12 , β -Bi 2 Mo 2 O 9 and γ -Bi 2 MoO 6 , prepared by the spray drying technique, is described and discussed. The structure of polycrystalline, layered samples investigated by means of XRD and Raman spectroscopy was found to be monoclinic for the α -and β -phases and orthorhombic for the γ -phase. The microstructure of the asprepared samples was not sufficiently developed under the given conditions of preparation, however, the thermal treatment can improve it. The high polarizability of Bi 3+ cations with their lone-pair electrons influences the stability of the disordered oxygen sublattice. All as-prepared phases undergo a slight structural change in the temperature region of 280-430°ë resulting in a decrease of the electrical conductivity probably due to an order disorder transition in the oxygen arrangement during the sample heating. The change of electrical conductivity observed was found to be reversible in the high-temperature region and irreversible in the lowtemperature one. The blocking of oxygen transport by the bismuth lone-pair electrons results in an increase of the activation energy and a decrease of the electrical conductivity in the high-temperature region. Relatively high relative dielectric permittivities ε r , 36-52, were observed in dependence on the investigated phase.