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The year 1975 can be claimed to be the year of inception for the research and development of solid polymer electrolytes (SPEs) for Lithium-Ion Batteries (LIB), when the ionic conductivity of polyethylene oxide–alkaline metal ion complex was found by Peter Wright from the University of Sheffield. However, SPE research has undergone a leapfrog development, with conductivity values improving from 1 × 10–7 S·cm−1 to 1 × 10– 1 S·cm−1. The seed of development of SPEs spurs from the need for introducing design freedom to battery structures as well as the need for leak-proof electrolytes, greater operational safety, higher energy density, and other considerations. While the benefits of SPEs are evident, poor interfacial contact is a major factor limiting their application. This review presents the history of SPEs and shows how the additive manufacturing (AM) could prove beneficial for the improvement of performance and the functional implementation of SPEs. While the article articulates a technical review of additively manufactured SPEs, it also provides a lab-to-market perspective that could aid in shaping the future of green technology in energy storage. It also aims to provide an overall picture about the evolution and diversity of research advances in the development of greener SPEs through AM technology.