An electrochemical characterization of a silver molybdenum oxyfluoride perovskite positive electrode for Li batteries was investigated as a function of synthesis condition, stoichiometry and effect of Mo and Ag derived second phases. A detailed in situ electrochemical study by XAS, Raman, and XRD was performed, revealing a 3 electron silver displacement or conversion reaction at >3V and a 2 electron reduction of Mo6+ to Mo4+ in the region <3V.