A novel aqueous lithium–air rechargeable cell with the configuration of Si/1 M LiClO4 in ethylene carbonate–diethylene carbonate/Li1+x+y Al x (Ti,Ge)2−x P3−y Si y O12/5 M LiCl–1 M LiOH aqueous solution/carbon black, air is proposed. A silicon anode composed of mechanically milled silicon power with an average particle size of ca. 0.5 μm, vapor grown carbon fiber and a polyimide binder was examined. The open-circuit voltage at the charged state was 2.9 V at 25 °C. The discharge capacity of 700 mAh g-silicon−1 was retained for 40 cycles at 0.3 mA cm−2 with cut-off voltages of 3.5 and 1.5 V. Significant capacity fade was observed at deep charge and discharge cycling at 2000 mAh g-silicon−1.