Silver vanadium oxide (SVO, Ag2V4O11) was synthesized in solid-state reactions from silver carbonate and silver metal powder starting materials with vanadium oxide (V2O5) as the vanadium source. These powders were prepared as primary cathode materials for lithium batteries. Thermal analyses of stoichiometric mixtures of V2O5 and silver sources were used to elucidate the mechanism of Ag2V4O11 formation. V2O5 reacts with Ag2CO3 in a two step decomposition/combination (DC) reaction. Weight gain measured by TGA during the reaction of Ag(0)+V2O5 in O2 indicated the formation of Ag2V4O11. XRD analysis of the synthesis products of the Ag(0)+V2O5 reaction indicated the formation of AgV2O5 under inert atmosphere and Ag2V4O11 under oxidizing (air or O2) conditions. The surface area and morphology of the materials were strongly influenced by the synthesis method, linked to the parameters of time, temperature, and reaction atmosphere. The electrochemical performance of the SVO cathode material also depended on the synthesis method, where SVO prepared from the DC reaction mechanism yielded improved long-term performance.