We carried out in-situ observation on the catalytic effect of Nb2O5 in MgH2 by using a high voltage transmission electron microscope (HVEM). We synthesized two kinds of samples, which were prepared by ball milling and by hand mixing. In milled sample, Nb2O5 was not confirmed from high resolution images, however, NbO was identified. As the temperature increased, the decomposition of MgH2 proceeded, while Mg formed and grew. It suggested that NbO had the catalytic effect to promote the dehydrogenation of MgH2. In mixed sample, which was prepared to clearly observe the boundary between the catalyst and Mg phase, it was revealed that the dehydrogenation started from the boundary of MgH2 and Nb2O5. This result suggested that the dehydrogenation could proceed with hydrogen diffusion from MgH2 through Mg phase to the boundary.