Polycrystalline LixV6O13 samples, 0.5≤x≤6, were prepared by chemical intercalation in n-butyl lithium and investigated spectroscopically by x-ray absorption, electron paramagnetic resonance (EPR), and 7Li solid state nuclear magnetic resonance (NMR). Both the EPR results and the vanadium K-edge x-ray absorption fine structure spectra show that the average oxidation state of the vanadium decreases with the addition of Li, and the x-ray results provide evidence of lithium deficient and oxygen deficient impurity phases. The local symmetry of the vanadium atoms first decreases with increasing x from 0≤x≤1 and then increases with increasing x as the vanadium octahedral environment becomes less distorted. These changes are revealed by both the intensity of the first V-O peak in the radial distribution function and by the decrease in the x-ray absorption pre-edge peak intensity. However, structural correlations beyond the nearest neighbor atoms rapidly decrease with increasing Li content above x=1.5, reflecting increased disorder. The observed increase in the V-O distance implies a modest lattice expansion with intercalated Li, from 1.93 Å at x=0 (in agreement with x-ray diffraction) to 2.11 Å at x=5. Variable temperature 7Li NMR linewidth and spin-lattice relaxation measurements demonstrate that dynamic processes govern the spin-lattice relaxation when 0.5≤x≤2, but paramagnetic and homonuclear dipolar interactions reduce the spin-lattice relaxation time as x is increased beyond 2. The 7- Li NMR lineshape confirms the presence of impurity phases. Paramagnetic and diamagnetic chemical shifts imply local magnetic ordering accompanying the structural changes on lithium intercalation. © 1998 American Institute of Physics.