Bi2Te3-based compounds are a well-known class of outstanding thermoelectric materials. β-As2Te3, another member of this family, exhibits promising thermoelectric properties around 400 K when appropriately doped. Herein, we investigate the high-temperature thermoelectric properties of the β-As2−xBixTe3 solid solution. Powder X-ray diffraction and scanning electron microscopy experiments showed that a solid solution only exists up to x = 0.035. We found that substituting Bi for As has a beneficial influence on the thermopower, which, combined with extremely low thermal conductivity values, results in a maximum ZT value of 0.7 at 423 K for x = 0.017 perpendicular to the pressing direction.