The complex hydride LiAlH4 doped with rare earths (RE) catalysts of LaCl3, CeCl3 and Ce(SO4)2, respectively were prepared by ball milling. The effects of RE catalysts on the dehydriding properties and phase structures of the complex hydride LiAlH4 were investigated. The results show that the doped Ce(SO4)2 has little effect on the dehydrogenation of LiAlH4 in the ball milling process. However, the doped LaCl3 and CeCl3 cause dehydrogenation of the partial LiAlH4, resulting in LiCl and Al3RE (RE=La, Ce). The doped RE catalysts decrease the dehydriging start temperature of LiAlH4, especially Ce(SO4)2, which decreases the dehydriging start temperature by about 25 oC. RE catalysts help to speed up the decomposition reaction rate of LiAlH4 and improve the dehydriding properties of LiAlH4