The valence-band and core-level soft x-ray photoelectron spectroscopy has been applied to investigate the origin of the large thermoelectric power in the off-stoichiometric and partially-substituted Fe-based Heusler-type alloys Fe 2-x-y Ir y V 1+x Al and Fe 2-x V 1+x-y Ti y Al. The non-rigid-band-like change in the valence-band electronic structure near the Fermi level E F is found for the off-stoichiometric change x in Fe and V concentrations, whereas the rigid-bandlike shift of E F is

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... ed on the Ir or Ti substitution y. The non-rigid-band-like change may be induced by the excess-V or Fe (anti-site defects)-derived states in the pseudogap of Fe 2 VAl, while the rigid-band-like shift may be caused by a common band formation, where the d states of the substituted elements are incorporated into the main Fe-V 3d bands. The V2p core-level spectra consistently show the satellite structure due to the excess V as the anti-site defect. A model electronic structure is presented for explaining the observed enhancement of their thermoelectric power.