Novel hexagonal rods of Bi 0.4 Sb 1.6 Se 3x Te 3(1−x) (0.0≤x≤1.0) were synthesized successfully through solid-state microwave synthesis. These hexagonal rods were explored using field emission scanning electron microscopy and transmission electron microscopy images. The X-ray diffraction results indicate that the powders (0.0≤x≤0.8) can be indexed as the rhombohedral phase, whereas the sample with x=1.0 has an orthorhombic phase structure. The hole concentration gradually decreases as Se increased, resulting in a decrease in electrical conductivity and an increase in the Seebeck coefficient. Ascribing to the increased Seebeck coefficient for the sample with x=0.8, the maximum power factor is 7.47mW/mK 2 at 373K.