Oxidation process of lanthanum hexaboride (LaB6) ceramic powder was investigated . The LaB6 powder samples were heated continually from room temperature to 1 473 K at a heating rate of 10 K/min by differential scanning calorimetry. The oxidation tests were conducted at different exposure temperatures. The phases and morphologies of the samples before and after exposure were analyzed by XRD and SEM. It was pointed out that before 1 273 K, LaB6 has high oxidation resistant ability, which was due to that the oxide layer hinders the oxygen diffusion from outer to the surface of LaB6 grains. The oxide layer was composed of the transition phases, which were composed of La2O3 and B2O3 formed from the initial oxidation; when the oxidation temperature exceeded 1 273 K, protective layer was destroyed due to the vaporization of liquid B2O3. Based on the results of X-ray diffraction analysis, oxidation process of LaB6 ceramic powder can be described as follows: Before 1 273 K, lanthanum borate，La(BO2)3 was formed on the surface of samples, then lanthanum oxide (La2O3) and boron oxide (B2O3) were present on the surface of samples oxidized when the temperature reached to 1 473 K.