Mesoporous single crystal (PSC) oxides have been reported as presenting higher electrochemical performances than bulk materials in lithium ion batteries operating via intercalation processes. Here, we extend this study to the electrochemical behaviour of mesoporous Cr2O3 versus Li+/Li0. We confirm that the Cr2O3 reacts towards Li through a conversion reaction mechanism leading, upon discharge, to the formation of large metallic chromium nanoparticles (10nm); the latter are embedded into a Li2O matrix together with, in this specific case, a copious amount of polymeric materials coming from electrolyte degradation, surrounding the particles, and filling the pores. During the following charge, re-oxidation of the nanoparticles occurs with the formation of CrO1−x , with the main difference, as opposed to bulk Cr2O3 electrodes, being the preservation of the polymeric layer at the end of the charge. We believe the material mesoporosity, via capillary effects, to be at the origin of such a difference. These electrolyte degradation products are shown to help in maintaining the material mesoporosity for a great number of cycles; and interestingly they are not detrimental to the cell performance in terms of capacity retention while presenting great advantages in terms of charge transfer by reducing diffusion lengths, namely for Li+ ions. The positive attributes of mesoporous material-based electrodes noticed for insertion reactions can then be extended to conversion reaction electrodes as long as we can master their synthesis while controlling their mesoporosity through either soft or hard templating techniques.