n-Type Bi 2Te 3–Bi 2Se 3 alloys with CdCl 2 and p-type Bi 2Te 3 + Sb 2Te 3 doped with 4 wt.% Te and were prepared by gas atomization and melt spinning processes, respectively, followed by sintering under vacuum. Microstructure and thermoelectric property of both the alloys were investigated as a function of doping quantity and sintering temperature from 400 to 500 °C, and compared with those of same alloys conventionally grown. Contrary to the microstructure formed in the directionally grown single crystal, no segregation of constituents like Te, Bi, Sb and Se was observed to form in the as rapidly solidified and sintered bodies. The highest thermoelectric figure of merit, calculated from the combination of Seebeck coefficient, electrical conduction, thermal conductivity, was obtained from the n-type specimen doped with 0.03 wt.% and sintered at 500 °C, while from the p-type sample sintered with the finest powders at 450 °C followed by annealed.