In this study, the strategies of modifying the electronic structure, tuning carrier concentration, and nanostructuring were implemented to improve the power factor and reduce the thermal conductivity of Si−Ge simultaneously. The Si 0.65−x Ge 0.32 Ni 0.03 B x (x = 0.01, 0.02, 0.03, and 0.04) nanostructure was synthesized by high-energy ball-milling. Subsequently, a highpressure with low-temperature sintering process was carried out. A small amount of nickel (Ni) and boron (B) was introduced into Si−Ge to modify the electronic structure and optimize the carrier concentration. The sintered sample Si 0.62 Ge 0.32 Ni 0.03 B 0.03 showed a high power factor of 2.3 mW m −1 K −2 at 1000 K, which was influenced by the modified electronic structure and optimized carrier concentration. In addition, the thermal conductivity was effectively decreased to 1.47 W m −1 K −1 due to the phonon scattering by the micro to nanoscale grain boundaries. Ultimately, a large dimensionless figure of merit ZT ∼1.56 was obtained at 1000 K. Therefore, following these strategies can improve the thermoelectric performance of earth-abundant, environmentally friendly, and nontoxic Si−Ge material.