The goal of this work is to unambiguously link nanoconfinement geometry of a layered host electrode material, bilayered V2O5, with the resulting electrochemical ion intercalation properties. For this purpose, model electrode materials with different, well-defined interlayer spacings are synthesized by employing alkyldiamines of various lengths that act as molecular pillars/spacers within the interlayer. As illustrated in Fig. , ethylenediamine (2C-DA), 1,6hexanediamine (6C-DA), or 1,12-dodecanediamine (12C-DA) are dissolved in water (water/ethanol mixture in case of 12C-DA for better solubility) together with commercially available α-V2O5 powder and undergo hydrothermal treatment at 100 °C for 12 hours in an autoclave. For further comparison, a reference sample with pre-intercalated Li + and H2O (Li-V2O5) is synthesized via a sol-gel process followed by hydrothermal treatment, as described by Clites et al. (Fig. and Fig. ). 1.21 nm (6C-DA) and 1.92 nm (12C-DA). Li-V2O5 synthesized via the sol-gel route exhibits the same crystal structure with a (001)-spacing of 1.22 nm (Fig. ), which is in the typical range of bilayered V2O5 materials with nanoconfined water and/or alkali cations. 7,11 A more detailed structural analysis of the bilayered V2O5 host structure is performed by highly localized transmission electron imaging/diffraction techniques, vide infra.