However, there are large gaps in the mechanistic understanding of the structure and electrochemistry of such pillared host materials. Importantly, the interaction between pillars and host material (e.g., covalent / ionic / non-bonding) and associated changes in the host crystal structure upon pillar insertion, the local configuration of pillars, and the structural and chemical stability of the pillars during electrochemical cycling need to be identified. Due to the simultaneous variation of various parameters, the differentiation of the impact of the individual parameters like nanoconfinement geometry on the material performance is challenging. Furthermore, there is also a lack of understanding of the dependence of the intercalated ions' diffusion paths from the d-spacing of the host material, as alternative pathways could become activated in an expanded interlayer space. Computational studies are required that determine the diffusion paths and associated energy barriers as a function of the host materials' nanoconfinement geometry. To provide clear mechanistic insights and to systematically answer the raised questions about molecularly pillared host materials, a well-defined model system is required, which can unambiguously link the modulated nanoconfinement geometry to the electrochemical ion intercalation properties. This work presents a series of molecularly pillared δ-V2O5alkyldiamine materials, which show a wide, systematic variation in interlayer spacing (1.0 -1.9 nm) owing to different lengths of diamine pillars. The model systems exhibit an identical, well-defined intralayer crystal structure where only the c-parameter of the host system is varied by the molecular pillars. The materials possess comparable nanowhisker-morphology, specific surface area, pillar chemistry, and pillar density in the interlayer. This allows to link the observed electrochemical Li + intercalation properties to the nanoconfinement geometry in the host interlayer, utilizing combined electrochemical operando experiments and computational investigation of Li + diffusion paths and associated energy barriers. The work gives direct insights into the structural requirements for favorable ion intercalation properties in pillared V2O5 hosts. Moreover, much needed insights into the structure-property relationships of pillared host materials with a well-defined nanoconfinement environment is provided, being of interest to a wide audience including electrocatalysis or selectivity .