The effects of CeCl3 and Ce(SO4)2 doping on the hydrogen-release capacity of NaAlH4 have been studied by pressure-composition-temperature equipment. The results show that the total amount and the rate of hydrogen release first increase and then decrease with increasing of CeCl3 and Ce(SO4)2 contents. The rate and the amount of decomposition for the sample doped with 4 mol% CeCl3 in the first-stage dehydrogenation processes are both better than those for the sample doped with 3 mol% Ce(SO4)2. The rate and the amount of decomposition at 110, 130, 150 and 180 °C present an obvious increase with increasing of temperature.