We have previously demonstrated polyimide (PI) gel polymer electrolyte (GPE)-based nanoencapsulation as a new surface modification strategy for high-voltage cathode materials. In this study, in an endeavor to attain a more comprehensive understanding of the PI GPE-based surface modification, effects of structural variation of PI encapsulating layers (specifically, focusing on PI coating thickness) on cell performance and thermal stability of high-voltage (4.4 V) LiCoO2 are investigated. Herein, PI coating thickness is tuned between approximately 10 and 40 nm by varying polyamic acid (synthesized from pyromellitic dianhydride/oxydianiline) concentration of coating solutions. As PI coating thickness is increased, discharge C-rate capability of cells is deteriorated due to undesired rise of ionic and electronic resistance of thick PI coating layers. On the other hand, thick PI encapsulating layers are effective in mitigating interfacial exothermic reaction between delithiated LiCoO2 and liquid electrolyte. Notably, among the various PI coating thicknesses, average thickness of 10 nm imparts well-balanced enhancement in cell performance and thermal stability. These results demonstrate that structural fine-tuning (particularly, coating thickness) of PI encapsulating layers, acting as ion-conductive protective conformal thin films, plays a significant role in optimizing their beneficial coating effects on high voltage LiCoO2. (C) 2012 Elsevier B.V. All rights reserved.