The advent of the lithium-ion batteries (LIBs) has transformed the energy storage field, leading to significant advances in electronics and electric vehicles, which continuously demand more and more performant devices. However, commercial LIB systems are still far from satisfying applications operating in arduous conditions, such as temperatures exceeding 100 °C. For instance, safety issues, materials degradation, and toxic stem development, related to volatile, flammable organic electrolytes, and thermally unstable salts (LiPF₆), limit the operative temperature of conventional lithium-ion batteries, which only occasionally can exceed 50–60 °C. To overcome this highly challenging drawback, the present study proposes advanced electrolyte technologies based on innovative, safer fluids such as ionic liquids (ILs). Among the IL families, we have selected ionic liquids based on tetrabutylphosphonium and 1-ethyl-3-methyl-imidazolium cations, coupled with per(fluoroalkylsulfonyl)imide anions, for standing out because of their remarkable thermal robustness. The thermal behaviour as well as the ion transport properties and electrochemical stability were investigated even in the presence of the lithium bis(trifluoromethylsulfonyl)imide salt. Conductivity measurements revealed very interesting ion transport properties already at 50 °C, with ion conduction values ranging from 10⁻³ and 10⁻² S cm⁻¹ levelled at 100 °C. Thermal robustness exceeding 150 °C was detected, in combination with anodic stability above 4.5 V at 100 °C. Preliminary cycling tests run on Li/LiFePO₄ cells at 100 °C revealed promising performance, i.e., more than 94% of the theoretical capacity was delivered at a current rate of 0.5C. The obtained results make these innovative electrolyte formulations very promising candidates for high-temperature LIB applications and advanced energy storage systems.