We reported on the hydrogen desorption properties, microstructure, kinetics, and chemical bonding state of catalyst surface for composites of MgH(2) and 1 mol% Nb(2)O(5) ball-milled for 0.02 h, 0.2 h, 2 h, 20 h under 1 MPa H(2) atmosphere, as well as hand-mixed (HM) one. Hydrogen desorption properties were significantly improved by ball-milling with Nb(2)O(5). Then, we estimated by Kissinger Method the activation energy (E(a)) of hydrogen desorption reaction that decreased with the increase of ball-milling time. Especially, E(a) of the sample ball-milled for 0.2 h was drastically decreased, compared with that of the sample ball-milled for 0.02 h. TEM observations revealed that the distribution of Nb(2)O(5) in MgH(2) was gradually improved during ball-milling. On the other hand, we confirmed by XPS that in the sample ball-milled for 0.2 h, Nb(2)O(5-x) phase(s) existed at least on the surface. It can be suggested that these deoxidized Nb(2)O(5-x) phases eventually decrease E(a) as substantial catalyst rather than Nb(2)O(5) itself. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.