We present the facile synthesis of crystalline V2O5 nanorods and V2O5/TiO2 nanocomposites structures by a carbon nanocage (CNC)-assisted growth process, using vanadium triisopropoxide oxide and titanium isopropoxide precursors in air at 500
C. The diameters of the resultant V2O5 nanorods ranged between 10 and 70 nm, while the crystalline V2O5/TiO2 nanocomposite structures adopted a unique morphology, due to both crystallisation and templating processes, with V2O5 adopting small-diameter nanowire and nanorod morphologies surrounded by sub-30 nm TiO2 nanoparticles. The V2O5 nanorods and V2O5/TiO2 nanocomposites were characterised by electron microscopy and X-ray diffraction techniques and subsequently reviewed as positive Li-ion electrodes. The phase-pure V2O5 nanorod structures exhibited appreciable Li+ storage properties over the potential range of 2.0–4.0 V vs. Li/Li+, displaying capacities of up to 288 mA h g1 with appreciable cyclic behaviour at test rates of up to 1 C. The crystalline V2O5/TiO2 nanocomposite structures displayed similar Li+ storage properties, however, increasing molar fractions of TiO2 led to a decline in the overall capacity versus the single-phase V2O5 counterparts. Interestingly, the Li+ insertion behaviour of the V2O5/TiO2 nanocomposite displayed character more-typical of amorphous V2O5, which was ascribed to a structural buffering effect of the inactive TiO2 phase.