This study mainly analyzed the effect of CeO2 on the hydrogen release capacity of LiAlH4 by PCT (Pressure-Composition-Temperature) device and SEM (Scanning Electron Microscope) analysis method. The results show that with CeO2 doping shortens markedly the time of hydrogen release of LiAlH4. Among all samples, the dehydrogenation time of the sample doped with 2 mol% CeO2 is the earliest. The study on the amount of hydrogen release finds that the sample doped with 1 mol% CeO2 presents the largest dehydrogenation amount. And with the increase of the doping amount from 1 mol% to 5 mol%, the total hydrogen release amount of the samples presents a decrease trend. Furthermore, the study on microstructures show that doping with CeO2 does not cause any obvious change of the microstructure of LiAlH4, and all samples show a kind of flocculent structure