The cycling stability of pillared V2O5 materials is probed by GCD at 0.5 A/g over 100 cycles and shown in Fig. . All samples show a significant initial capacity decay over ca. 5-10 cycles and a slow but linear capacity reduction over the next 90 cycles, which is in line with other reports on lithium (de)intercalation in V2O5. To probe whether the capacity decay is a consequence of the V2O5 host structure or disintegrating pillaring structure, ex situ XRD measurements of electrodes after 50 cycles are presented (Fig. ). The diffractograms show that the initial interlayer spacing is retained, demonstrating that alkyldiamine pillars remain in the V2O5 structure. Consequently, future work with a focus on practical application will include the transfer of this pillaring approach to host systems that exhibit higher intrinsic cycling stability than bilayered V2O5, which is known for a limited long-term stability of Li + intercalation. electrochemical cell at 2.0 V vs. Li + /Li. Instead of the highly expanded d-spacing found during the operando experiment, a much smaller d-spacing of ca. 1.5 nm is found for the lithiated electrode in the ex situ setting (Fig. ). It was previously found that co-intercalated solvent molecules are highly volatile and quickly evaporate upon removal of the electrode from the electrochemical cell. Thus, the significant reduction of measured d-spacing for V2O5-12C-DA in the ex situ experiment compared to the operando setting is supportive of the cointercalation mechanism hypothesis because of solvent evaporation from the nanoconfined interlayer space. An alternative explanation for the observed d-spacing of V2O5-12C-DA in the lithiated state is a change of the 12C-DA pillars' tilt angle arrangement to αi of 62° (according to Fig. ), however, such a change in pillar tilt angles is not observed for 2C-DA or 6C-DA making this explanation less likely in our estimation.