Here, we investigate the physicochemical and electrochemical properties of fluorine-free ionic liquid (IL)-based electrolytes with two different cations, tetrabutylphosphonium, (P_4,4,4,4)⁺, and tetrabutylammonium, (N_4,4,4,4)⁺, coupled to a new anion, 2-[2-(2-methoxyethoxy)ethoxy]acetate anion (MEEA)−, for both neat and (P_4,4,4,4)(MEEA) also doped with 10–40 mol % of Li(MEEA). We find relatively weaker cation–anion interactions in (P_4,4,4,4)(MEEA) than in (N_4,4,4,4)(MEEA), and for both ILs, the structural flexibility of the oligoether functionality in the anion results in low glass transition temperatures, also for the electrolytes made. The pulsed field gradient nuclear magnetic resonance (PFG NMR) data suggest faster diffusion of the (MEEA)− anion than (P_4,4,4,4)⁺ cation in the neat IL, but the addition of a Li salt results in slightly lower mobility of the former than the latter and lower ionic conductivity. This agrees with the combined ⁷Li NMR and attenuated total reflection–Fourier transform infrared (ATR–FTIR) spectroscopy data, which unambiguously reveal preferential interactions between the lithium cations and the carboxylate groups of the IL anions, which also increased as a function of the lithium salt concentration. In total, these systems provide a stepping stone for further design of fluorine-free and low glass transition temperature IL-based electrolytes and also stress how crucial it is to control the strength of ion–ion interactions.