© 2018 Elsevier Inc. High-symmetry thermoelectric materials usually have the advantage of very high band degeneracy, while low-symmetry thermoelectrics have the advantage of very low lattice thermal conductivity. If the symmetry breaking of band degeneracy is small, both effects may be realized simultaneously. Here we demonstrate this principle in rhombohedral GeTe alloys, having a slightly reduced symmetry from its cubic structure, to realize a record figure of merit (zT ∼ 2.4) at 600 K. This is enabled by the control of rhombohedral distortion in crystal structure for engineering the split low-symmetry bands to be converged and the resultant compositional complexity for simultaneously reducing the lattice thermal conductivity. Device ZT as high as 1.3 in the rhombohedral phase and 1.5 over the entire working temperature range of GeTe alloys make this material the most efficient thermoelectric to date. This work paves the way for exploring low-symmetry materials as efficient thermoelectrics. Thermoelectric materials enable a heat flow to be directly converted to a flow of charge carriers for generating electricity. The crystal structure symmetry is one of the most fundamental parameters determining the properties of a crystalline material including thermoelectrics. The common belief currently held is that high-symmetry materials are usually good for thermoelectrics, leading to great efforts having historically been focused on GeTe alloys in a high-symmetry cubic structure. Here we show a slight reduction of crystal structure symmetry of GeTe alloys from cubic to rhombohedral, enabling a rearrangement in electronic bands for more transporting channels of charge carriers and many imperfections for more blocking centers of heat-energy carriers (phonons). This leads to the discovery of rhombohedral GeTe alloys as the most efficient thermoelectric materials to date, opening new possibilities for low-symmetry thermoelectric materials. Cubic GeTe thermoelectrics have been historically focused on, while this work utilizes a slight symmetry-breaking strategy to converge the split valence bands, to reduce the lattice thermal conductivity and therefore realize a record thermoelectric performance, all enabled in GeTe in a rhombohedral structure. This not only promotes GeTe alloys as excellent materials for thermoelectric power generation below 800 K, but also expands low-symmetry materials as efficient thermoelectrics.