Polyethylene oxide (PEO)-based composite electrolytes (PCEs) are considered as the promising candidates for next generation lithium metal batteries due to its high safety, easy fabrication and good electrochemical stability. However, the material suffers from low conductivity and high crystallinity of the ethylene oxide (EO) chain, which inhibits its commercialization. Therefore, it is crucial to understand the electrochemcial process as well as Li+ transfer pathway within PEO-based batteries. Using operando grazing-incidence small-angle and wide-angle X-ray scattering (GISAXS and GIWAXS) in Li||Cu cell framework, we find that the electrochemical reaction within the PCE is highly correlated with the evolution of the buried morphology and crystalline structure evolution of the PCE. This two irreversible reactions, PEO-Li+ reduction and TFSI- decomposition, cause changes in both the crystalline structure and morphology of the PCE. In addition, the reversible Li plating/stripping process alters the inner morphology, especially the PEO-LiTFSI domain radius, rather than causing crystalline structure changes. This work provides a new path to monitor a working battery in real time, thereby enabling detailed understanding of electrochemically-induced changes of the microscopic morphology and crystalline structure of PCE, which is essential for developing high transferable and interface stable PCE-based lithium metal batteries. Figure 1