Bilayered V2O5 materials are synthesized with three different nanoconfinement geometries by using alkyldiamine pillars with variable lengths. The structural investigation demonstrates that they exhibit highly comparable morphology, surface area, intralayer crystal structure, density of pillaring molecules in the interlayer, and ionic pillar-host interaction. Hence, they are suitable as model electrode materials to analyze the impact of the nanoconfinement geometry / interlayer spacing on the electrochemical Li + intercalation reaction, because influences of other structural features on the electrochemical signal remain negligible across the three samples.