First-principles calculations within the framework of Density Functional Theory (DFT) are conducted to gain a deeper understanding of the thermodynamics and kinetics involved in the Li + intercalation process in bilayered V2O5 intercalation hosts as a function of their nanoconfinement geometry, i.e., interlayer spacing. In our preliminary model construction, we adopt the crystal structure observed for V2O5•nH2O again according to the model of Petkov et al. As described in the structural characterization section, this structure exhibits bilayers of V2O5 arranged in a stacking fashion along the c-axis within a monoclinic unit cell (space group C2/m). These layers are composed of square pyramidal VO5 units as shown in Fig. .