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Single crystals of V6O13 were grown by chemical vapour transport (CVT) and subsequently electrochemically lithiated. The title compound, trilithium hexavanadium tridecaoxide, was the phase formed during electrochemical lithiation at 2.45 V versus Li/Li+. The Li3V6O13 structure comprises single and double layers of VO6 octahedra stacked in the c direction. Lithiation results in a 6.5% expansion along the b axis with respect to V6O13. Lithium is located in two crystallographic independent sites: a fully occupied 4i site with fivefold square-pyramidal O-atom coordination [Li-O distances in the range 1.960 (1)-2.031 (5) Å]; and one 50% occupied 4i site with planar quadratic O-atom coordination [Li-O distances in the range 1.99 (1)-2.08 (5) Å].