Abstract Substitution of oxygen by fluorine in a bismuth vanadium zinc oxide belonging to the BIMEVOX family has allowed the synthesis of a mixed anion (O, F) phase which can be considered as the first member of a new BIIMEVOF family. As for the corresponding BIZNVOX phase, three different forms (α, β and γ) have been identified, depending upon the composition and the temperature. The high temperature γ form can be stabilized down to room temperature for a lower Zn content than in the oxide derivatives. X-ray diffraction, thermal analysis and density measurements have been used to confirm that fluorine partly substitutes oxygen leading to the formation of the solid solution: Bi 2V 1− x− y Zn x Bi y O 5.5−2.5 x− y F 2 x . The evolution of electrical conductivity with fluorine ratio has been investigated by impedance spectroscopy.