Silicon-air battery utilizing a single-crystal heavily doped n-type silicon wafer anode and an air cathode is reported in this paper. The battery employs hydrophilic 1-ethyl-3-methylimidazolium oligofluorohydrogenate [EMI·(HF)2.3F] room temperature ionic liquid electrolyte. Electrochemical studies, including polarization and galvanostatic experiments, performed on various silicon types reveal the predominance performance of heavily doped n-type. Cell discharging at constant current densities of 10, 50, 100 and 300μAcm−2 in ambient atmosphere, shows working voltages of 1.1–0.8V. The study shows that as discharge advances, the moist interface of the air electrode is covered by discharge products, which prevent a continuous diffusion of oxygen to the electrode–electrolyte interface. The oxygen suffocation, governed by the settlement of the cell reaction products, is the main factor for an early failure of the cells. Based on the results obtained from scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy studies, we propose a series of reactions governing the discharge process in silicon-air batteries, as well as a detailed mechanism for silicon oxide deposition on the air electrode porous carbon.