In-situ transmission electron microscopy (TEM) has been performed to observe decomposition process of sodium alanate (NaAlH4) in this work. NaAlH4 was ground in a glove box under inert gas, and then it was transferred into microscope without exposed to air by Plastic Bag Method. The results of in-situ electron beam diffraction showed that NaAlH4 decomposed to Na3AlH6 + Al, and NaH + Al during heated up to 150 and 200 degrees C, respectively. Moreover, we obtained the result of high-resolution (HR) TEM images about the decomposition of NaAlH4 by high voltage electron microscopy (HVEM) of 1250 key. It showed that the porous structures appeared with increase of temperature. This should be from structural defects and/or cavities due to volume change of the phases. It was also shown that Na3AlH6 and Al particles with the grain size of several 10 nm were irregularly distributed near the pores. (C) 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.