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Li 7 La 3 Zr 2 O 12 (LLZO)-based solid-state Li batteries (SSLBs) have emerged as one of the most promising energy storage systems due to the potential advantages of solid-state electrolytes (SSEs), such as ionic conductivity, mechanical strength, chemical stability and electrochemical stability. However, there remain several scientific and technical obstacles that need to be tackled before they can be commercialised. The main issues include the degradation and deterioration of SSEs and electrode materials, ambiguity in the Li + migration routes in SSEs, and interface compatibility between SSEs and electrodes during the charging and discharging processes. Using conventional ex situ characterization techniques to unravel the reasons that lead to these adverse results often requires disassembly of the battery after operation. The sample may be contaminated during the disassembly process, resulting in changes in the material properties within the battery. In contrast, in situ / operando characterization techniques can capture dynamic information during cycling, enabling real-time monitoring of batteries. Therefore, in this review, we briefly illustrate the key challenges currently faced by LLZO-based SSLBs, review recent efforts to study LLZO-based SSLBs using various in situ / operando microscopy and spectroscopy techniques, and elaborate on the capabilities and limitations of these in situ / operando techniques. This review paper not only presents the current challenges but also outlines future developmental prospects for the practical implementation of LLZO-based SSLBs. By identifying and addressing the remaining challenges, this review aims to enhance the comprehensive understanding of LLZO-based SSLBs. Additionally, in situ / operando characterization techniques are highlighted as a promising avenue for future research. The findings presented here can serve as a reference for battery research and provide valuable insights for the development of different types of solid-state batteries.