In this study, an oxide reduction process and a reduction-sintering process were employed to synthesize a thermoelectric alloy from three thermoelectric composite oxide powders, and the thermoelectric properties were investigated as a function of the milling duration. Fine grain sizes were analyzed by via X-ray diffraction and scanning electron microscopy, to investigate the influence of the milling duration on the synthesized samples. It was found that microstructural changes, the Seebeck coefficient, and the electrical resistivity of the compounds were highly dependent on the sample milling duration. Additionally, the carrier concentration considerably increased in the samples milled for 6 h; this was attributed to the formation of antisite defects introduced by the accumulated thermal energy. Moreover, the highest value of ZT (=1.05) was achieved at 373K by the 6-h milled samples. The temperature at which the ZT value maximized varied according to the milling duration, which implies that the milling duration of the three thermoelectric composite oxide powders should be carefully optimized for their effective application.