This study investigated the effect of Nd2O3 and Gd2O3 as catalyst on hydrogen desorption behavior of NaAlH4. Pressure-content-temperature (PCT) equipment measurement proved that both two oxides enhanced the dehydrogenation kinetics distinctly and increasing Nd2O3 and Gd2O3 from 0.5 mol% to 5 mol% caused a similar effect trend that the dehydrogenation amount and average dehydrogenation rate increased firstly and then decreased under the same conditions. 1 mol% Gd2O3-NaAlH4 presented the largest hydrogen desorption amount of 5.94 wt% while 1 mol% Nd2O3-NaAlH4 exerted the fastest dehydrogenation rate. Scanning Electron microscopy (SEM) analysis revealed that Gd2O3-NaAlH4 samples displayed uniform surface morphology that was bulky, uneven and flocculent. The difference of Nd2O3-NaAlH4 was that with the increasing of Nd2O3 content, the particles turned more and more big. Compared to dehydrogenation behavior, this phenomenon demonstrated that small particles structure were beneficial to hydrogen desorption. Besides, the further study found that different catalysts and addition amounts had different effects on the microstructure of NaAlH4. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.