Hybrid organic–inorganic perovskites have generated considerable research interest in the field of optoelectronic devices. However, there have been significantly fewer reports of their thermoelectric properties despite some promising early results. In this article, we investigate the thermoelectric properties of bismuth-doped CH3NH3PbBr3 (MAPbBr3) single crystals. The high-quality Bi-doped crystals were synthesized by inverse temperature crystallization and it was found that Bi substitutes onto the B-site of the ABX3 perovskite lattice of MAPbBr3 crystals with very little distortion of the crystal structure. Bi doping does not significantly alter the thermal conductivity but dramatically enhances the electrical conductivity of MAPbBr3, increasing the charge carrier density by more than three orders of magnitude. We obtained a negative Seebeck coefficient of −378 μV K−1 for 15% (x = 0.15) Bi-doped MAPb(1−x)BixBr3 …