Thermodynamic stability and hydrogen occupancy on the hydrogen+tetra-n-butyl ammonium fluoride semi-clathrate hydrate have been investigated by means of phase equilibrium (pressure-temperature) measurements and Raman spectroscopic analyses for two mole fractions, 0.018 and 0.034 (stoichiometric for the cubic structure) of tetra-n-butyl ammonium fluoride aqueous solutions. In the case of higher concentration (0.034), the stability boundary curve of hydrogen+tetra-n-butyl ammonium fluoride semi-clathrate hydrate locates at about 23 K higher temperature than that of hydrogen+tetrahydrofuran mixed gas hydrate. The storage capacity of hydrogen in the cubic structure for the hydrogen+tetra-n-butyl ammonium fluoride semi-clathrate hydrate is smaller than that of hydrogen+tetrahydrofuran mixed gas hydrate. In the case of hydrate prepared from the lower concentration (0.018) of aqueous solution, the Raman spectra and phase behavior reveal that the cubic structure of semi-clathrate hydrate is changed to a different one at about 9 MPa and 299.2 K. The new structure can entrap larger amount of hydrogen than the cubic one. The stability boundary curve of hydrogen+tetra-n-butyl ammonium fluoride semi-clathrate hydrate obtained in the aqueous solution of lower mole fraction (0.018) is shifted to slightly low-temperature or high-pressure side from that of higher mole fraction (0.034). (c) 2008 Elsevier Ltd. All rights reserved.