1 M LiPF6 dissolved in oligo(ethylene glycol) dimethyl ether with a molecular weight 500 g mol−1 was investigated as a new electrolyte (OEGDME500, 1 M LiPF6) for metal deposition and battery applications. At 25 °C a conductivity of 0.48 × 10−3 S cm−1 was obtained and at 85 °C, 3.78 × 10−3 S cm−1. The apparent activation barrier for ionic transport was evaluated to be 30.7 kJ mol−1. OEGDME500, 1 M LiPF6 allows operating temperature above 100 °C with very attractive conductivity. The electrolyte shows excellent performance at negative and positive potentials. With this investigation, we report experimental results obtained with aluminum electrodes using this electrolyte. At low current densities lithium ion reduction and re-oxidation can be achieved on aluminum electrodes at potentials about 280 mV more positive than on lithium electrodes. In situ X-ray diffraction measurements collected during electrochemical lithium deposition on aluminum electrodes show that the shift to positive potentials is due to the negative Gibbs free energy change of the Li–Al alloy formation reaction.