Vanadium oxide aerogels were used as a precursor for preparing nanotextured VO2[B] by low-temperature heat treatment under vacuum. The VO2[B] material retains the fibrous morphology and high surface area of the aerogel. Evolution of the VO2[B] phase, as studied by FTIR and X-ray diffraction, indicates that the local structure of the vanadium oxide aerogel is close to that of VO2[B], in agreement with the bilayer-type structure previously proposed for vanadium oxide aerogels/xerogels. The electrochemical behavior of VO2[B] also bears similarity to that of vanadium oxide aerogels. Specific capacities for lithium as high as 500 mA·h/g are obtained for nanocrystalline VO2[B], and stable electrochemical response is obtained when cycled between 4 and 2.4 V vs Li+/Li0.