Deformation electron density refinement of single-crystal X-ray data has been performed for V6O13 and for one of its electrochemically lithiated phases Li2V6O13. The electron rearrangement associated with lithium insertion is extracted by subtracting the two derived electron deformation models from one another. The reduction (from nominally V5+ to V4+) Of one of the three independent vanadium atoms (V2) in the asymmetric unit can be identified, along with significant changes in the effective charges on certain of the oxygens.