The hydrogen solubility and the hydrogen permeability of pure niobium at high temperature are investigated in order to analyze the hydrogen diffusion coefficient during the hydrogen permeation. It is shown that the hydrogen dissolution reaction into niobium metal does not follow the Sieverts' law at the practical hydrogen permeation pressures. The hydrogen diffusion coefficient during the hydrogen permeation through pure niobium at high temperature is evaluated from the linear relationship between the normalized hydrogen flux, J.d, and the hydrogen concentration difference, Delta C. It is found that the hydrogen diffusion coefficient under the practical condition is much lower than the reported values measured for dilute hydrogen solid solutions. Surprisingly, the hydrogen diffusion is found to be faster in Pd-Ag alloy with fcc crystal structure than in pure niobium with bcc crystal structure at 773 K during the hydrogen permeation. (C) 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.