A series of composite electrolytes (CEs) consisting of organic/inorganic hybrid star-shaped polymer (SPP13), plasticizer (PEG-functionalized PUSS derivatives), and lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) were prepared to investigate the effects of the composite compositions and PEG chain length of PEs on the properties of CEs. SPP13 was prepared via ATRP from poly(ethylene glycol) methyl ether methacrylate (PEGMA) and methacryl-cyclohexyl-POSS (MA-PUSS) using an octafunctional initiator, and the PEG-functionalized PUSS derivatives were synthesized by the hydrosilylation reaction of octakis(dimethylsilyloxy)silsesquioxane (OHPS) and allyl-PEG. The CEs were found to be dimensionally-stable enough to separate the electrodes in batteries, but they still possessed high mobility of ion-conducting P(PEGMA) segments, as estimated by the low glass transition temperatures (T-g). The CEs having solid-state show quite high ionic conductivity (4.5 x 10(-5) S cm(-1) at 30 degrees C) which is about three times of magnitude larger than that of the matrix polymer (SPP13) electrolyte (1.5 x 10(-5) S cm(-1) at 30 degrees C). The CEs were electrochemically stable up to +4.2 V without the decomposition of electrolytes. An all-solid-state lithium battery prepared from the CEs exhibited larger discharge capacity than that prepared from the SPP13 electrolyte at 60 degrees C. (C) 2013 Elsevier Ltd. All rights reserved.