The α-NaFeO 2 structure-type oxides, such as LiNiO 2 , LiCoO 2 , and α-LiAlO 2, could not only provide channels for Li + conduction but also conduct protons through intercalation. However, the detailed conduction mechanism of protons in the layer structure oxide needs to be further distinguished. In this work, we prepared layered-oxide α-Li 0.88 AlO 2 and used it as an electrolyte to assemble a solid oxide fuel cell (SOFC), which delivered an output of 1046 mW cm −2 at 550 °C, a decent power output is ascribed to the excellent ion conductivity (0.2 S cm −1 ) and low activation energy (0.36 eV) of the α-Li 0.88 AlO 2 electrolyte. Moreover, the H/ D isotope experiments revealed that the proton dominated the ion conduction of α-Li 0.88 AlO 2. First-principles calculations indicate that the special structure-layered oxides provide channels that allow protons to transfer rapidly with low activation energy. This work indicates the possibility of using layered oxides as proton conductors in a low-temperature SOFC (LT-SOFC) and reveals the proton transport mechanism in oxides, it provides a new approach to exploit novel electrolytes for LT-SOFC.