Herein we report the first study of the electrochemical reduction of a high Ag/V ratio silver vanadium phosphorous oxide, Ag3.2VP1.5O7.8. Based on XRD, magnetic susceptibility, AC impedance and conductivity data, a three step mechanism is proposed. The initial reduction by 2.0 electron equivalents is consistent with the reduction of Ag+ to Ag-0 accompanied by a 9 order of magnitude increase in conductivity and decrease in AC impedance. From 2.0 to 3.0 electron equivalents, the reduction of vanadium begins in parallel with Ag+ to Ag-0 reduction. Continuation of reduction past 3.0 electron equivalents leads to further reduction of the vanadium center. Lithium cells based on Ag3.2VP1.5O7.8 cathodes showed promising performance attributes including significant delivered capacity above 3.0 V,and good performance under pulse conditions. (C) 2013 The Electrochemical Society. All rights reserved.