Sintering processes yield a mutual diffusion region at the electrode/solid electrolyte interface, which is considered as a crucial problem for developing large-sized all-solid-state rechargeable lithium batteries with high power density. This work focuses on the interface between LiNi1/3Co1/3Mn1/3O2 (NMC) and NASICON-structured Li+ conductive glass ceramics solid electrolyte (Li2OAl2O3 SiO2 P2O5 TiO2 GeO2: LATP sheet (AG-01)), and investigates the effects of sintering temperature on interfacial structure and interfacial resistance at the NMC/LATP sheet. Thin films of NMC were fabricated on the LATP sheets at 700 °C or 900 °C as a model system. We found that the thickness of the mutual diffusion region was almost the same, ca. 30 nm, in these two samples, but the NMC film prepared at 900 °C had three orders of magnitude larger interfacial resistance than the NMC film prepared at 700 °C. Around the interface between the NMC film prepared at 900 °C and the LATP sheet, Co in the NMC accumulates as a reduced valence and lithium-free impurity crystalline phase will be also formed. These two problems must contribute to drastic increasing of interfacial resistance. Formation of de-lithiated NMC around the interface and its thermal instability at higher temperature may be considerable reason to induce these problems.