The phase-formation processes in the Bi2O3-V 2O5 and Bi2O3-MO-V2O 5 (M = Zn, Pb, Cu, Co, Ni) systems were investigated. The associated sequence of phase transformations and the conditions for preparing single-phase Bi4V2O11 (Bi2VO5.5) and Bi2V1 - xMexO5.5 - 3x/2 solid solutions were established. The lattice parameters of the solid solutions were determined, and their conductivity was measured as a function of temperature and composition.