The polymorph phase stability ranges have been studied for the Bi4V2-xMexO11-y solid solutions with Me = Ga and Zr at room temperature. The formation of orthorhombic α- (x = 0.0 and 0.05) and β-phases (x = 0.1, 0.15) and tetragonal phase (0.2 ≤ x ≤ 0.3) has been revealed in BIGAVOX solid solutions. In BIZRVOX solid solutions, α-phase exists at x ≤ 0.05, while β-phase exists at 0.1 ≤ x ≤ 0.3. The second order phase transitions at ~ 308°C (BIGAVOX) and ~ 270°C (BIZRVOX) have been revealed for solid solutions with x = 0.05 using the SHG and DSC methods. In both systems, the β↔γ-phase transition temperatures have been found to decrease with increasing x.