All-solid-state Li/LiPONB/TiOS microbatteries were manufactured at the pilot scale on silicon substrate. In a first attempt, the characterization of the active materials constituting the microbattery was achieved in order to determine their accurate composition, structure and morphology. Finally, a thorough electrochemical characterization was carried out on all-solid-state cells. Excellent performances were noted in terms of cycle life (with more than 1000 cycles), efficiency and self-discharge (less than 5% per year). In addition, the positive electrode highlighted a high volumetric capacity close to 90μAhcm−2 μm−1 when cycled at 100μAcm−2 between 1V and 3V vs. Li+/Li.