Herein we report the effect of Cu/In doping on the electronic and thermal transport properties of Bi-Sb-Te thermoelectric alloys. To closely examine the role of each doping element when incorporated in a Bi 0.4 Sb 1.6 Te 3 alloy, different groups of samples were prepared and characterized, including undoped Bi 0.4 Sb 1.6 Te 3 , In single-doped samples and In and Cu doped ones. It was observed that Cu and In had different impacts on the thermoelectric properties of the Bi 0.4 Sb 1.6 Te 3 . For example, the Hall carrier concentration of Bi 0.4 Sb 1.6 Te 3 was increased by Cu doping and decreased by In doping while maintaining Hall mobility, which suggests that the physical parameters related to the thermoelectric transport can be carefully controlled by doping with Cu and In. In addition, we found that the electronic structure of Bi 0.4 Sb 1.6 Te 3 can be modified by Cu/In doping. The density of states effective mass (m * ) value of the Cu-doped sample (1.07 m 0 ) was increased. However, the m * of the In-doped sample (0.85 m 0 ) was decreased compared to the pristine sample (0.97 m 0 ). Cu single-doped Bi 0.4 Sb 1.6 Te 3 exhibited the maximum thermoelectric figure-of-merit because of the complexity of substitutional doping on Bi/Sb sites. Our results indicate that to enhance the performance of thermoelectric materials by doping with more than one element a well-designed doping strategy is required.