The Li-ion battery has served as the workhorse of many industries for a generation. The technology has advanced incrementally over the years, but the underlying chemistry has undergone only minimal changes since its commercialization in the early 90’s. A novel solvent-free polymer electrolyte developed by Ionic Materials, Inc. threatens to shift this paradigm. The polymer electrolyte is based on a crystalline thermoplastic polymer which is treated with an oxidizing agent and then reacted with a lithium salt. This electrolyte displays transport properties suitable for commercial battery use, while retaining the mechanical and safety advantages associated with a solid, and sufficient electrochemical stability to allow its use with Li-metal and high voltage intercalation electrodes. We report here Nuclear Magnetic Resonance (NMR) investigations of this polymer electrolyte. Pulsed-field gradient self-diffusion studies, in tandem with relaxometry and magic angle spinning (MAS), allow characterization of the structure and dynamics of this revolutionary material. Our measurements show room-temperature Li⁺ self-diffusion coefficients on the order of 10^-9 m²/s (an order of magnitude higher than previously reported solid electrolyte candidates), as well as cation transference numbers approaching 0.5. We have also established further evidence that the ionic motion is decoupled from polymer segmental or chain motion, in contrast to the mechanism governing ionic transport in the widely studied polyether-based electrolytes. We discuss some of the challenges of studying this material, as well as the implications of the results for its suitability as an electrolyte for secondary Li metal batteries.