The structural behaviour of the sol-gel chromium-vanadium mixed oxide Cr0.11V2O5.16 is investigated as electrochemical lithium insertion proceeds. Electrochemically reduced electrodes are examined by XRD over the large Li composition range 0 < x <= 2 in LixCr0.11V2O5.16. New fingerprints of lithiated phases are obtained in comparison with available data in the Li-V2O5 system. It is shown that lithiation produces an -related phase over a wide composition range 0.18 <= x <= 2 whose interlayer distance linearly increases with x which strongly contrasts with the successive appearance of the (alpha/epsilon), (epsilon/delta), and (delta/gamma) wide biphasic regions for the LixV2O5 system. The existence of shorts chains of CrO6 octahedra perpendicular to V2O5 layers increases the three-dimensional character of the host lattice impeding then too strong deformations to occur. Thesse limited structural changes resulting in a single phase behaviour are discussed in relation with the original and promising electrochemical properties of the sol-gel mixed oxide Cr0.11V2O5.16. (C) 2010 Elsevier B.V. All rights reserved.