Structural differences in [V2Te2O10](n)(2n-) chain metrics are directly ascribed to variations in noncovalent interactions in a series of organically templated vanadium tellurites, including [C6H17N3][V2Te2O10].H2O, [C5H16N2][V2Te2O10], and [C4H14N2][V2Te2O10]. The noncovalent interaction (NCI) method was used to locate, quantify, and visualize intermolecular interactions in [C4H14N2][V2Te2O10] and [C5H16N2][V2Te2O10]. Variations in the van der Waals attractions between [1,4-diaminobutaneH2](2+) and [1,5-diaminopentaneH(2)](2+) result in divergent packing motifs for these cations, which causes a reorganization of N-H...O hydrogen bonding and variances in the [V2Te2O10](n)(2n-) chain metrics. The application of the NCI method to this type of solid-state structure provides a direct method to elucidate the structural effects of weak noncovalent interactions.