NaAlH4 has a theoretical hydrogen capacity of 5.6 wt. % with two-step reaction, and the control of the reaction temperature and reversibility is a critical issue for onboard application. To clarify nano-structural details of decomposition of NaAlH4, the in-situ annealing experiment was carried out in a high resolution microscope. It was confirmed that NaAlH4 decomposed at between 200 and 300°C, resulted in formation of many gas bubbles at interface between the particle and oxide film. A reactive intermediate, Na3AlH6, may decompose in this temperature range. Sodium alanate particle was originally agglomeration of small nano-sized crystal with the size of 10 – 20 nm, and the crystal grain grew to 110 nm in diameter after completing decomposition at around 400°C. This is the first step for examination of the microstructural response of catalysts on hydrogen storage materials.