In this work, the properties of silver-modified LiMn2O4 cathode materials are revisited. We study the influence of calcination atmosphere on the properties of the Ag-coated LiMn2O4 (Ag/LMO) and highlight the silver oxidation. The effect of the heat treatment in vacuum is compared with that in air by the characterization of the structure, specific surface area, Li transport properties and electrochemical performance of Ag/LMO composites. Surface analyses (XPS and Raman spectroscopy) show that the nature of the coating (~3 wt.%) differs with the calcination atmosphere: Ag/LMO(v) calcined in vacuum displays Ag nanospheres and minor AgO content on its surface (specific surface area of 4.1 m2 g−1), while Ag/LMO(a) treated in air is mainly covered by the AgO insulating phase (specific surface area of 0.6 m2 g−1). Electrochemical experiments emphasize that ~3 wt.% Ag coating is effective to minimize the drawbacks of the spinel LiMn2O4 (Mn dissolution, cycling instability, etc.). The Ag/LMO(v) electrode shows high capacity retention, good cyclability at C/2 rate and capacity fade of 0.06% per cycle (in 60 cycles).