Abstract: GeTe is a thermoelectric material with excellent performance and is considered a promising candidate for commercial applications in the medium-temperature range due to its high thermoelectric efficiency and environmental adaptability; however, the presence of Ge enrichment in GeTe results in a low intrinsic zT. To improve the thermoelectric properties of germanium telluride, GeTe was prepared by the hot-pressing method and iron was doped to enhance its thermoelectric properties and to further observe and evaluate its material properties. First-principles calculations were applied to analyze its electronic structure and energy bands, the crystal microstructure was obtained using electron microprobe (EBS), and the variation of thermal conductivity with crystal structure was analyzed. Both simulations and thermoelectric measurements show that Fe doping can promote the optimization of the energy band structure and increase the phonon scattering of germanium telluride, which can significantly improve the thermoelectric properties of germanium telluride, and the resulting sample has the best thermoelectric properties after doping with 2% Fe powder by mass, with the highest thermoelectric optimum (zT) value of about 1.57 at a temperature of 680 K, which is approximately 50% higher than that of intrinsic GeTe. Fe is an ideal thermoelectric material for GeTe, as the thermal performance has been greatly improved by optimizing the thermal conductivity.