The maximum specific capacity for Li + intercalation in the host materials at low rate is between 155 -193 mAh/g. Subtracting the mass contribution of (electrochemically) inactive pillaring molecules, the lithium ion storage capacity per V2O5 is increased with larger interlayer spacing, with an improvement from approx. 1.0 to 1.5 Li + in the material with the intermediate expansion. Furthermore, the rate handling improves with larger interlayer spacings. This demonstrates the possibility of improving ion storage capacity and kinetics in layered host materials by manipulating the nanoconfinement geometry. Density functional theory investigations explain the kinetic properties by a change in diffusion mechanism from 1D towards networks of 2D diffusional pathways for Li + when increasing the interlayer spacing of V2O5 hosts. Operando X-ray diffraction investigation reveals a solid-solution Li + intercalation mechanism with minimal reversible expansion/contraction behavior for V2O5 hosts with small (V2O5-2C-DA) and intermediate (V2O5-6C-DA) interlayer spacing. For V2O5 with the largest interlayer spacing (V2O5-12C-DA), an abrupt further expansion is observed. We hypothesize this is due to the simultaneous intercalation of electrolyte solvent (ion-solvent cointercalation mechanism). This demonstrates the dependence of the charge storage mechanism on the host material's nanoconfinement geometry.