The cycling characteristics of lithium (Li) secondary electrode with an Al substrate have been investigated in sulfolane (S)‐based electrolytes. The cycling efficiency varied with the charge‐discharge conditions: the cycling charge and the cycling rate (current density). The efficiency also depended on the blended cosolvent ether and on the electrolytic salt. The highest efficiency was obtained in the system of . The Li cycling characteristics on the Al substrate were compared with those on the Ni substrate. The current efficiency for the electroplating of Li on the substrates suggested that the coulombic loss of the efficiency on the Al substrate was mainly caused by the insufficient plating of Li during the charge while the loss at the Ni substrate was based on some undesirable chemical reaction of plated Li with the electrolyte.