AgSbTe₂compounds have been synthesized via melting and subsequent cooling processes. The effect of cooling process, from air-cooling, water quenching to liquid nitrogen-quenching, on the microstructure and the electrical transport properties of AgSbTe₂has been investigated by means of powder X-ray diffraction, electron microscope, electrical resistivity, and Hall coefficient measurements. It has been found that the cooling process has apparent influence on the microstructure and corresponding electrical properties. The phase components and morphology changed as the cooling process altered. The electrical resistivity and the Seebeck coefficient of the as-prepared samples increased from air-cooled to liquid nitrogen-quenched sample.