For battery architectures that need a solid ion conductor with good contacting performance and high stability against electrochemical oxidation, polymerized ionic liquids (PIL) pose a valuable class of materials. The low conductivity of the binary PIL/ lithium salt system can be increased using a ternary ionic liquid acting as plasticiser. The conductive mechanism of the ternary system is however not fully understood. This work shows the shift in conduction mechanism for the ternary Li−/[1,3]PYR-/PDADMA-FSI system by increasing the lithium salt concentration and comparing the transfer mechanism to binary ionic liquid (IL) electrolyte analogues using pulsed field gradient (PFG) nuclear magnetic resonance (NMR), NMR relaxometry, Raman spectroscopy and electrochemical techniques. Two conducting regimes were found which show a strong trade-off between conductivity and transference number. In the low lithium salt regime (≤35 wt% LiFSI), cluster diffusion of aggregated lithium is the dominating mechanism leading to low transference numbers (0.04–0.15 at room temperature (RT)). The high salt regime (≥50 wt% LiFSI) shows diffusion through free lithium ion hopping transfer, which has a stronger dependence on temperature and yields higher transference numbers (0.31 at RT). Increasing lithium salt concentration shows an inverse linear correlation with conductivity. The electrochemical characteristics of ternary IL/PIL/lithium salt are shown to be highly tuneable by varying the lithium salt fraction, while it maintains excellent characteristics like processability, stability and mechanical function.