Single thermite-type combustion synthesis (STCS) for synthesizing Heusler alloy Fe 2 VAl from Fe, V 2 O 5 , and Al powders for thermoelectric applications was proposed and investigated, in which the microstructure and the thermoelectric properties of the product were mainly examined. Macroscopically, STCS was successfully carried out to produce metallic product of Fe 2 VAl in lower part and alumina as slag in upper part. According to SEM observation and FE-EPMA-analyzed, elemental mapping images, the product contained dispersed inclusions of spherical Al 2 O 3 with 0.4mol% and angulated AlN with 1.0mol%. In comparison to the reported data on Fe 2 VAl, the thermal conductivity at room temperature became about half. It could be because of increased phonon scattering due to dispersed AlN&Al 2 O 3 and non-stoichiometry of the product; Fe 2.06 V 1.01 Al 0.93 . As a result, the maximum values for the product were 99.6μWm −1 K −2 in power factor and 2.19×10 −3 at 309K in dimensionless figure of merit.