An advanced electrochemical characterization of cross-linked ternary solid polymer electrolytes (SPEs), prepared by a solvent-free hot-pressing process, is reported. Ionic conductivity, electrochemical stability window and limiting current measurements were performed as a function of the temperature by using both potentiodynamic and galvanostatic techniques. Additionally, the lithium cycleability was evaluated with respect to its dependence on both the operating temperature and the current density by using a new multi-rate Li-stripping-plating procedure. The results clearly indicate the beneficial effect of higher operating temperatures on the rate-capability, without major degradation of the electrochemical stability of the SPE. All-solid-state lithium metal polymer batteries (LMPBs), comprising a lithium metal anode, the cross-linked ternary solid polymer electrolyte and a LiFePO4 composite cathode, were manufactured and investigated in terms of the interdependencies of the delivered capacity, operating temperature and discharge rate. The results prove quite exceptional delivered capacities both at medium current densities at ambient temperatures and even more impressive capacities above 160mAhg−1 at high discharge rates (1C) and temperatures above 60°C.