The nanowhiskers of high aspect ratio are found to be a few tens of nanometers wide and a few up to tens of micrometers long. Overall, the nanowhisker morphology of all samples is similar. This is a significant requisite to correlate the electrochemical Li + intercalation performance to the nanoconfinement geometry of the model materials, given that the morphology may have a significant influence on the electrochemical properties of V2O5. While sharing an unambiguous nanowhisker morphology with the (001) basal planes being systematically aligned parallel to the long whisker dimension (Fig. ), significant differences of interlayer spacing are revealed between the samples, attributed to the successful pillaring of the bilayered V2O5 host structure using alkyldiamine of three lengths. This is concluded from powder X-ray diffraction (XRD), selected-area electron diffraction (SAED) and high-resolution TEM (HRTEM) analyses (Figs. , respectively). Complementary to the XRD, the crystal structure of the samples is confirmed by powder SAED of representative whisker ensembles. All three samples present a monoclinic crystal structure of the space group C2/m characteristic of such bilayered δ-V2O5 systems. Comparing simulated with measured SAED pattern of the three samples, it becomes clear that a systematic increase in the (001) lattice spacing from 0.95 nm to 1.10 nm to 1.50 nm is observed for 2C-DA, 6C-DA and 12C-DA, respectively (Fig. ). However, the prominent SAED signals corresponding to (020) and (110) planes are identical for all samples, demonstrating no pillar-induced alteration of inplane host structure (Fig. ). It should be noted that the smaller (001)-spacing derived from TEM analysis compared to XRD analysis may likely result from partial pillar degradation under the high energy electron beam and/or loss of confined interlayer species under vacuum conditions, although measures like minimal-dose imaging/diffraction were applied. Nonetheless, the basal planes are continuous, well aligned and extend along the whole whisker. Moreover, the interlayer spacing within individual whiskers appears to be constant.