Single crystals of V6O13 were grown by chemical vapour transport and then electrochemically lithiated. The title compound, dilithium hexavanadium tridecaoxide, was the first phase formed during electrochemical lithiation at 2.65 V versus Li/Li+. The Li2V6O13 structure can be described as layers of VO6 octahedra stacked perpendicular to the c direction. Lithiation causes a 7.6% expansion along the c axis. The lithium ions occupy positions with fivefold square-pyramidal oxygen coordination between the layers.