Many elements have been used as dopants to enhance the thermoelectric performance of Bi2Te3 -related materials. Among them, Ag's effect on thermoelectric properties, where Ag acts as a donor or acceptor, remains unclear. To elucidate the role of Ag in n-type Bi2Te3 based compounds, Ag was added to n-type (Bi0.9Sb0.1)(2)(Te0.85Se0.15)(3). As the amount of Ag was increased, the electron concentration decreased, which means Ag acted as an acceptor. The added Ag atoms were found to occupy interstitial sites in the hexagonal lattices, as confirmed by X-ray analysis and first principles calculations. The reduction in electron concentration was attributed to the interaction between the interstitial Ag and intrinsic defects.