The structural behaviour of the sol–gel chromium–vanadium mixed oxide Cr 0.11V 2O 5.16 is investigated as electrochemical lithium insertion proceeds. Electrochemically reduced electrodes are examined by XRD over the large Li composition range 0 < x ≤ 2 in Li x Cr 0.11V 2O 5.16. New fingerprints of lithiated phases are obtained in comparison with available data in the Li–V 2O 5 system. It is shown that lithiation produces an ɛ-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 (α/ɛ), (ɛ/δ), and (δ/γ) wide biphasic regions for the Li x V 2O 5 system. The existence of shorts chains of CrO 6 octahedra perpendicular to V 2O 5 layers increases the three-dimensional character of the host lattice impeding then too strong deformations to occur. These 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 Cr 0.11V 2O 5.16.