Silver hollandite (Ag1.4Mn8O16) has been synthesized by an aqueous, low-temperature co-precipitation technique to afford silver hollandite with distinct crystallite sizes (10 and 15 nm, identified as S-Ag1.4Mn8O16 and L-Ag1.4Mn8O16, respectively) and equivalent silver content (x), allowing for the deconvolution of electrochemical effects related to crystallite size and silver content. The as-prepared silver hollandite materials were confirmed to be structurally analogous. Notably, TEM imaging reveals a high degree of bundling of S-Ag1.4Mn8O16 nanorods compared to L-Ag1.4Mn8O16 which facilitates more intimate connection of the S-Ag1.4Mn8O16 material with enhanced interparticle contact. The electrochemical behavior and lithium diffusion properties were investigated by galvanostatic cycling, CV, electrochemical impedance, pulsed-discharge experiments, and ex-situ XAS analysis of cycled cathodes. Lithium based electrochemical cells containing S-Ag1.4Mn8O16 delivered a capacity 15X higher than L-Ag1.4Mn8O16 on cycle 1. Ex-situ XAS demonstrated structural change for S-Ag1.4Mn8O16 and formation of Ag-0 on insertion of 3.8 Li+ intercalation. However, the samples of L-Ag1.4Mn8O16 were lithiated by a more limited 0.25 molar equivalents, where no significant structural changes were observed. The findings affirm crystallite size significantly impacts electrochemistry independent of cation occupancy of the alpha-MnO2 type structure. (c) 2017 The Electrochemical Society. All rights reserved.