All-solid-state batteries promise significant safety and energy density advantages over liquid-electrolyte batteries. The interface between the cathode and the solid electrolyte is an important contributor to charge transfer resistance. Strong bonding of solid oxide electrolytes and cathodes requires sintering at elevated temperatures. Knowledge of the temperature dependence of the composition and charge transfer properties of this interface is important for determining the ideal sintering conditions. To understand the interfacial decomposition processes and their onset temperatures, model cathode systems of LiCoO2 (LCO) and LiNi0.6Mn0.2Co0.2O2 (NMC622) thin films deposited on cubic Al-doped Li7La3Zr2O12 (LLZO) pellets were studied as a function of temperature, gas composition and electrochemical conditions. The methods combine interface-sensitive techniques, including X-ray photoelectron spectroscopy (XPS), synchrotron X-ray absorption spectroscopy, hard X-ray photoemission (HAXPES), and synchrotron X-ray diffraction. In this talk, we will present the found precipitation products at the interface as a function of synthesis and electrochemical conditions, their role in altering the interface resistance to Li transfer, and compare the LCO and NMC related cathodes in terms of their instability onset conditions. Results in particular indicate the importance of the selected temperature and gas conditions in giving rise to more stable interfaces, with fast Li transfer between the garnet electrolyte and the oxide cathodes.