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A solid-state electrolyte with reliable electrochemical performance, mechanical robustness and safety features is strongly pursued to facilitate the progress of flexible batteries. Here, we demonstrate a shape-deformable and thermally stable plastic crystal composite polymer electrolyte (denoted as "PC-CPE") as a new class of solid-state electrolyte to achieve this challenging goal. The PC-CPE is composed of UV (ultraviolet)-cured ethoxylated trimethylolpropane triacrylate (ETPTA) macromer/close-packed Al2O3 nanoparticles (acting as the mechanical framework) and succinonitrile-mediated plastic crystal electrolyte (serving as the ionic transport channel). This chemical/structural uniqueness of the PC-CPE brings remarkable improvement in mechanical flexibility and thermal stability, as compared to conventional carbonate-based liquid electrolytes that are fluidic and volatile. In addition, the PC-CPE precursor mixture (i.e., prior to UV irradiation) with well-adjusted rheological properties, via collaboration with a UV-assisted imprint lithography technique, produces the micropatterned PC-CPE with tunable dimensions. Notably, the cell incorporating the self-standing PC-CPE, which acts as a thermally stable electrolyte and also a separator membrane, maintains stable charge/discharge behavior even after exposure to thermal shock condition (=130 °C/0.5 h), while a control cell assembled with a carbonate-based liquid electrolyte and a polyethylene separator membrane loses electrochemical activity. [ABSTRACT FROM AUTHOR]