Sulfide-based all-solid-state batteries using a non-flammable inorganic solid electrolyte are promising candidates as a next-generation power source owing to their safety and excellent charge–discharge cycle characteristics. In this study, we thus focus on the positive electrode and investigated structural stabilities of the interface between the positive electrode active material LiNi1/3Mn1/3Co1/3O2 (NMC) and the 75Li2S·25P2S5 (LPS) glass electrolyte after charge–discharge cycles via transmission electron microscopy (TEM). To evaluate the thermal stability of the fabricated all-solid-state cell, in-situ TEM observations for the positive electrode during heating are conducted. As a result, structural and morphological changes are detected in the LPS glasses. Thus, exothermal reaction present in the NMC-LPS composite positive electrode after the initial charging is attributable to the crystallization of LPS glasses. On the basis of a comparison with crystallization behavior in single LPS glasses, the origin of exothermal reaction in the NMC-LPS composites is discussed.