Step potential electrochemical spectroscopy data of lithium anode cells using VSe2-ySy(0 less than or equal to y less than or equal to 0.5) compounds as cathode material and LiClO4 solutions in PC as electrolyte were studied. On increasing y, a lower extension of the intercalation process was observed, due to the loss of a second insertion step corresponding to lithium ion occupancy of tetrahedral sites. In contrast, the reaction rate increased with sulfur content. VSe2-y/LiCoO2 lithium-ion cells were cycled to test the electrochemical behaviour of the vanadium chalcogenides as anodic material. A better capacity retention was observed for y = 0.3. The effect of current density on the performance of the cells was also evaluated.