Li-ion batteries have been gaining increasing importance, driven by the growing utilization of renewable energy and the expansion of electric vehicles. To meet market demands, it is essential to ensure high energy density and battery safety. All-solid-state batteries (ASSBs) have attracted significant attention as a potential solution. Among the advantages, they operate with an ion-conductive solid electrolyte instead of a liquid electrolyte therefore significantly reducing the risk of fire. In addition, by using high-capacity alternative electrode materials, ASSBs offer a promising opportunity to enhance energy density, making them highly desirable in the automotive and secondary battery industries. In ASSBs, Li metal can be used as the anode, providing a high theoretical capacity (3860 mAh/g). However, challenges related to the high interfacial resistance between Li metal and solid electrolytes and those concerning material degradation during charge-discharge cycles need to be addressed for the successful commercialization of ASSBs. This review introduces and discusses the interfacial reactions between Li metal and solid electrolytes, along with research cases aiming to improve these interactions. Additionally, future development directions in this field are explored.