Effect of Au (0-0.3 wt.%) on the thermoelectric properties of Bi1Sb3Te6 alloy prepared by mechanical alloying process has been investigated. The Seebeck coefficient decreases with Au content. The Seebeck coefficient of Au-free alloy at room temperature reaches a value of 250 µV/K, which is the maximum. Because of the increased power factor, the figure of merit increases with Au content up to 0.03 wt. % and its value at room temperature is about 2.8×10-3/K, the highest value among the prepared alloys. The Hall measurement shows that the carrier concentration increases with Au content, which explains the reason why the power factor has increased. The XRD patterns show that the intensities of (2 0 5), (0 0 18), (0 2 10), (1 0 19), (1 2 5), and (2 1 10) planes increase with Au content. The atomic distance of these complex planes is longer than that of other main planes, and the chemical bonding strength of these complex planes between constitutional elements is weaker than that of other main planes. As a result, a portion of electrons as minor carrier is trapped into accept level of Au atoms and/or clusters. The XPS observation result, which a portion of Au atoms is chemically shifted in contrast to Bi, Sb and Te atoms are not, explains that Au behaves as an acceptor.