The e.m.f. vs. composition relationship of Li/Li_xV₆O₁₃ has been studied at 25 °C and 155 °C by cyclic voltammetry using organic and polymeric electrolytes, respectively. At both temperatures the lithium insertion reaction is found to be reversible in the composition interval: 0 ⩽, x ⩽ 8. a.c.- impedance measurements on single crystals (25 °C) show that Li⁺ diffusion in Li_xV₆O₁₃ is one dimensional and proceeds along the channels in the b axis direction. Cycling of Li/Li_xV₆O₁₃ cells with organic and polymer electrolyte shows that high materials utilization and good cycling performance can be achieved with both systems. It is demonstrated that Li_xV₆O₁₃ is sensitive to discharge below 1 V vs. Li.