1 M LiPF6 dissolved in oligo(ethylene glycol) dimethyl ether with a molecular weight, 500 g mol−1 (OEGDME500, 1 M LiPF6), was investigated as an electrolyte in experimental Al–Li/LiFePO4 cells. More than 60 cycles were achieved using this electrolyte in a Li-ion cell with an Al–Li alloy as an anode sandwiched between two LixFePO4 electrodes (cathodes). Charging efficiencies of 96–100% and energy efficiencies of 86–89% were maintained during 60 cycles at low current densities. A theoretical investigation revealed that the specific energy can be increased up to 15% if conventional LiC6 anodes are replaced by Al–Li alloy electrodes. The specific energy and the energy density were calculated as a function of the active mass per electrode surface (charge density). The results reveal that for a charge density of 4 mAh cm−2 about 160 mWh g−1 can be reached with Al–Li/LiFePO4 batteries. Power limiting diffusion processes are discussed, and the power capability of Al–Li/LiFePO4 cells was experimentally evaluated using conventional electrolytes.