A binary ionic liquid (IL) system based on a common cation, N-methyl-N-propylpyrrolidinium (C3mpyr+), and either bis(trifluoromethanesulfonyl)imide (NTf2−) or bis(fluorosulfonyl) imide (FSI−) as the anion is explored over its entire composition range. Phase behavior, determined by DSC, shows the presence of a eutectic temperature at 247 K and composition around an anion ratio of 2:1 (FSI−:NTf2−) with the phase diagram for this system proposed (under the thermal conditions used). Importantly for electrochemical devices, the single phase melting transition at the eutectic is well below ambient temperatures (247 K). To investigate the effect of such anion mixing on the lithium ion speciation, conductivity and PFG–NMR diffusion measurements were performed in both the binary IL system as well as the Li-NTf2-containing ternary system. The addition of the lithium salt to the mixed IL system resulted in a decrease in conductivity, as is commonly observed in the single-component IL systems. For a fixed lithium salt composition, both conductivity and ion diffusion have linear behaviour as a function of the anion ratio, however, the rate of change of the diffusion coefficient seems greater in the presence of lithium. From the application point of view, the addition of the FSI− to the NTf2− IL results in a considerable increase in lithium ion diffusivity at room temperature and no evidence of additional complex ion behaviour.