All-solid-state lithium/sulfur (Li/S) battery is prepared using siloxane cross-linked network solid electrolyte at room temperature. The solid electrolytes show high ionic conductivity and good electrochemical stability with lithium and sulfur. In the first discharge curve, all-solid-state Li/S battery shows three plateau potential regions of 2.4 V.2.12 V and 2.00 V. respectively. The battery shows the first discharge capacity of 1044 mAh g(-1)-sulfur at room temperature. This first discharge capacity rapidly decreases in 4th cycle and remains at 512 mAh g(-1)-sulfur after 10 cycles. (C) 2012 Elsevier Ltd. All rights reserved.