A detailed electrochemical study is presented of the lithium ion transport in polyphosphazene based gel polymer electrolytes. The polyphosphazene poly[bis(2-(2-methoxyethoxy) ethoxy) phosphazene (MEEP) was chosen for the polymeric network. In combination with liquid electrolytes (organic carbonates with lithium bis(oxalato) borate and lithium(hexafluoro) phosphate) gel polymer electrolyte membranes with very good ionic conductivities of 2.3mScm−1 at 30°C and high lithium transference numbers of 0.31 at 90°C were prepared. The investigated electrolytes exhibited very good interface stability at lithium metal electrodes during long term lithium plating/stripping experiments with up to 500 cycles. Discharge rate investigations on full cells consisting of lithium metal ∣ MEEP gel polymer ∣ LiFePO4 delivered high capacities of 140mAhg−1 at a discharge rate of 5C.