This work highlights a room-temperature composition study of the Ag2O/V2O5/HF(aq) ternary system, leading to the precipitation of either various silver vanadates having Ag/V ratios from 1/2 to 3/1 or the new silver vanadium oxyfluoride compounds Ag4V2O6F2 and Ag3VO2F4, and a synthetic procedure that affords nanocrystalline Ag2V4O11 (SVO) at room temperature. The as-precipitated SVO particles exhibit an acicular morphology, 10-15 x 50-200 nm in size, and present a peculiar reactivity vs lithium notably through a Ag+/Li+ displacement reaction that progresses in a reversible fashion. This step forward thus enables the reversible and simultaneous combination of two active redox processes (silver and vanadium), providing a significant enhancement in the cathode gravimetric capacity of 320 mAh/g at C rate and more than 250 mAh/g at 5C.