We study the complex mixture of a polyethylene oxide-b-polypropylene oxide-b-polyethylene oxide triblock copolymer (Pluronic F127) with ionic liquid (IL) and Li-salt, which is potentially interesting as an electrolyte system with decoupled mechanical and ion-transport properties. Small-angle X-ray scattering (SAXS) and differential scanning calorimetry (DSC) are employed to scrutinize the phase structures and elucidate the ternary phase diagram. These data are combined with the ion diffusivities obtained by pulsed field gradient (PFG) nuclear magnetic resonance (NMR). Analyzing the partial ternary phase diagram of F127/LiTFSI/Pyr 14 TFSI, hexagonal, lamellar, and micellar mesophases are identified, including two-phase coexistence regions. 'While the PPO block is immiscible with the liquid, and forms the backbone of the mesostructured aggregates, the PEO blocks are not well miscible with the IL. Poorly solvated, the latter may still crystallize. At a higher IL content, PEO is further solvated, but a major solvation effect occurs due to addition of Li-salt. Li ions promote solubilization of the PEO chains in the IL, since they coordinate to the PEO chains. This was identified as the mechanism of a transition of the mesostructures, with increasing Li-salt content changing from a hexagonal to a lamellar and further to a micellar phase. In summary, both, the amount of IL and its compatibility with the PEO block, the latter being controlled by the Li-salt amount, influence the compositions of the formed mesophases and the ion diffusion in their liquid regions.