A series of bilayered V2O5 host materials with well-defined interlayer spacings between 1.0-1.9 nm is synthesized. This is owing to the introduction of alkyldiamine molecular pillars of different lengths. Detailed structural characterization, including high resolution TEM at length scales relevant to the hosts' nanoconfinement geometries, reveals the structural properties of pillared V2O5 in detail. The materials exhibit comparable nanowhisker morphology, intralayer crystal structure, specific surface area, tilted pillar conformation and ionic hostpillar interaction, thus only varying in c-lattice parameter. This allows to unambiguously link their functional properties to the variation of nanoconfinement geometry.