Sodium aluminum hydride (NaAlH4) was directly synthesized by ball milling NaH/Alco-doped with CeCl3 + KH under a hydrogen pressure of 3 MPa at room temperature. Out of various samples corresponding to xNaH/Al + 0.02CeCl(3) + yKH (x + y = 1; y = 0, 0.02, 0.04 mol%) composites, the composite with y = 0.02 exhibits the optimum de/hydrogenation properties. It shows that the addition of KH can effectively improve the dehydrogenation properties of second step reaction of NaAIH(4) system. The composite with y = 0.02 starts to release hydrogen from 87 degrees C and completes dehydrogenation within 20 min at 170 degrees C, with good cycling de/hydrogenation kinetics at relatively lower temperature (100-140 degrees C). After ball milling, the CeCl3 precursor can be changed into CeH2 catalytic active component in the first several de/hydrogenation cycles. Apparent activation energy of the second decomposition step of NaAlH4 system can be effectively decreased by addition of KH, resulting in the decrease of desorption temperatures. Based on the microstructure analyses combined with hydrogen storage performances, the improved dehydrogenation properties of sodium aluminum hydride system are ascribed to the lattice volume expansion of Na3AlH6 during the dehydrogenation process resulted from the addition of KH. Moreover, by analyzing the reaction kinetics of CeCl3 + KH co-doped sample, both of the decomposition steps of composite with y = 0.02 were conformed to the two-dimension phase-boundary growth mechanism. The mechanistic investigations gained here could help to understand the de/rehydrogenation behaviors of catalyzed complex metal hydride systems. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.