We investigated that the effect of the number of segregated Li atoms on the rate of oxidation on a LiAl alloy surface. Oxygen molecules adsorbed on the LiAl alloy react with the surface atoms to form stable oxides. The segregated Li atoms at reconstructed surfaces (c(2×2) and (2×1)) enhance the oxidation rate and form stable LiAlOx and Li2O. The degree of enhancement of oxidation by segregated Li atoms varies as a function of O2 exposure and annealing temperature, where the latter is directly related to the mode of surface reconstruction by Li segregation.