The recent discovery of highly conductive solid-state electrolytes (SSEs) has led to tremendous progress in the development of all-solid-state batteries (ASSBs). Though promising, they still face barriers that limit their practical application, such as poor interfacial stability, scalability challenges and production safety. Additionally, efforts to develop sustainable manufacturing of lithium ion batteries are still lacking, with no prevailing strategy developed yet to handle recyclability of ASSBs. To date, most SSE research has been largely focused on the discovery of novel electrolytes. Recent review articles have extensively examined a broad spectrum of these SSEs using evaluation factors such as conductivity and chemical stability. Recognizing this, in this Review we seek to evaluate SSEs beyond conventional factors and offer a perspective on various bulk, interface and nanoscale phenomena that require urgent attention within the scientific community. We provide a realistic assessment of the current state-of-the-art characterization techniques and evaluate future full cell ASSB prototyping strategies. We hope to offer rational solutions to overcome some major fundamental obstacles faced by the ASSB community, as well as potential strategies toward a sustainable ASSB recycling model.