AbstractLithium-sulfur (Li–S) system coupled with thin-film solid electrolyte as a novel high-energy micro-battery has enormous potential for complementing embedded energy harvesters to enable the autonomy of the Internet of Things microdevice. However, the volatility in high vacuum and intrinsic sluggish kinetics of S hinder researchers from empirically integrating it into all-solid-state thin-film batteries, leading to inexperience in fabricating all-solid-state thin-film Li–S batteries (TFLSBs). Herein, for the first time, TFLSBs have been successfully constructed by stacking vertical graphene nanosheets-Li2S (VGs-Li2S) composite thin-film cathode, lithium-phosphorous-oxynitride (LiPON) thin-film solid electrolyte, and Li metal anode. Fundamentally eliminating Li-polysulfide shuttle effect and maintaining a stable VGs-Li2S/LiPON interface upon prolonged cycles have been well identified by employing the solid-state Li–S system with an “unlimited Li” reservoir, which exhibits excellent long-term cycling stability with a capacity retention of 81% for 3,000 cycles, and an exceptional high temperature tolerance up to 60 °C. More impressively, VGs-Li2S-based TFLSBs with evaporated-Li thin-film anode also demonstrate outstanding cycling performance over 500 cycles with a high Coulombic efficiency of 99.71%. Collectively, this study presents a new development strategy for secure and high-performance rechargeable all-solid-state thin-film batteries.