All-solid-state Li-ion batteries having incombustible solid electrolytes are expected to be promising candidates for safe next-generation energy storage devices that have a long lifetime and high energy density. However, it is essential to address the large resistance of Li-ion transfer at the electrode/solid-electrolyte interfaces. A new concept electrode that is formed in situ from the Li2O–Al2O3–TiO2–P2O5-based glass-ceramic solid electrolytes with Si and Ge doping (LASGTP) produces atomic scale connection at the interfaces, which provides extremely low interfacial resistance. However, the formation mechanism and the reason for the low resistance are still unclear. Here we applied spatially-resolved electron energy-loss spectroscopy in a transmission electron microscope mode (SR-TEM-EELS) to visualize the nanometer-scale Li distribution and its effects on the electronic structures of other important elements (Ti and O). Local electron diffraction showed that the in situ formed electrode was an amorphous phase caused by the Li insertion. Picometer-scale expansion of O–O distance due to the Li insertion was also visualized in the electrode. These electronic and crystal changes and gradual Li distribution contribute to the low resistance and stable battery cycles.