The article deals with the optimization of an anode based on commercial manganese oxide. Several parameters are considered in order to enhance capacity, rate capability and long-term cycleability. Particularly, Polyacrylic Acid as a green binder with enhanced mechanical features is proposed, while Vinylen Carbonate is added to a standard carbonate-based electrolyte system in order to enhance the stability of passivation layer and of electrode/electrolyte interface. The role of a reversible “gel-like” layer toward interfacial stability is investigated as well. Several structural, morphological and electrochemical investigation techniques are applied in order to fully characterize the behavior of baseline and modified electrodes and cells. This process results in an optimized system able to deliver, in a half-cell vs. metal Li, specific capacity values up to 725mAhg−1 at 1C-rate, stable for 100 cycles, and relevant rate capability, confirming a major influence of electrode and electrolyte formulation toward electrochemical performance.