Tetragonal FeAl 2 is a high-pressure phase and is predicted to exhibit semiconductor-like behavior. We investigated the pressure and temperature synthesizing conditions of tetragonal FeAl 2 , supported by in situ X-ray diffractions, using synchrotron radiation during heating the sample under a pressure of 20 GPa. Based on the determined optimal conditions, we synthesized the bulk polycrystalline samples of tetragonal FeAl 2 at 7.5 GPa and 873 K, using a multi-anvil press and measured its thermoelectric properties. The Seebeck coefficient of tetragonal FeAl 2 showed a large negative value of -105 μV/K at 155 K and rapidly changed to a positive value of 75 μV/K at 400 K. Although these values are the largest among those of Fe-Al alloys, the maximum power factor remained at 0.41 mW/mK 2 because the carrier concentration was not tuned. A comparison of the Gibbs free energy of tetragonal FeAl 2 , triclinic FeAl 2 and FeAl+Fe 2 Al 5 revealed that tetragonal FeAl 2 became unstable as the temperature increased, because of its smaller contribution of vibrational entropy.Temperature, T / K Pressure, P / GPa ARTICLE HISTORY