The study investigates the improved thermoelectric performance of elemental tellurium (Te) doped with group-VA elements (As, Sb, and Bi). Despite these dopants forming precipitates rather than dissolving in the Te lattice, they significantly enhance the electrical conductivity and power factor of bulk Te. The research employs a correlative method to locally determine the structure-property relationship for individual matrix or precipitate phases. It reveals that the dopant-induced metavalently bonded telluride precipitates form beneficial interfaces with the Te matrix, leading to a notable improvement in thermoelectric properties. The study also provides a material design map based on quantum-mechanical-derived bonding information, suggesting new telluride dopants with metavalent solids. This unconventional doping scenario opens new avenues for designing thermoelectric materials and microstructures.The study investigates the improved thermoelectric performance of elemental tellurium (Te) doped with group-VA elements (As, Sb, and Bi). Despite these dopants forming precipitates rather than dissolving in the Te lattice, they significantly enhance the electrical conductivity and power factor of bulk Te. The research employs a correlative method to locally determine the structure-property relationship for individual matrix or precipitate phases. It reveals that the dopant-induced metavalently bonded telluride precipitates form beneficial interfaces with the Te matrix, leading to a notable improvement in thermoelectric properties. The study also provides a material design map based on quantum-mechanical-derived bonding information, suggesting new telluride dopants with metavalent solids. This unconventional doping scenario opens new avenues for designing thermoelectric materials and microstructures.