This study addresses the challenges of dendrite growth and chemical corrosion in zinc (Zn) microbatteries, particularly in microscale applications. The authors introduce a photolithographable electrolyte that incorporates caffeine into a UV-crosslinked polyacrylamide hydrogel, enhancing Zn reversibility and stability. Caffeine passivates the Zn anode, preventing chemical corrosion and forming a Zn-rich interphase that improves cycling performance. In on-chip microbatteries, the Zn||MnO₂ full cell demonstrates over 700 cycles with an 80% depth of discharge (DOD). The electrolyte is also integrated into multilayer microfabrication, creating a 3D Swiss-roll microbattery with a footprint of 0.136 mm², maintaining 75% capacity over 200 cycles at a 90% DOD. This approach offers a promising solution for enhancing the performance of Zn microbatteries, particularly for on-chip microscale devices.This study addresses the challenges of dendrite growth and chemical corrosion in zinc (Zn) microbatteries, particularly in microscale applications. The authors introduce a photolithographable electrolyte that incorporates caffeine into a UV-crosslinked polyacrylamide hydrogel, enhancing Zn reversibility and stability. Caffeine passivates the Zn anode, preventing chemical corrosion and forming a Zn-rich interphase that improves cycling performance. In on-chip microbatteries, the Zn||MnO₂ full cell demonstrates over 700 cycles with an 80% depth of discharge (DOD). The electrolyte is also integrated into multilayer microfabrication, creating a 3D Swiss-roll microbattery with a footprint of 0.136 mm², maintaining 75% capacity over 200 cycles at a 90% DOD. This approach offers a promising solution for enhancing the performance of Zn microbatteries, particularly for on-chip microscale devices.