A new series of Ba2–xBixCoRuO6 (0.0 ≤ x ≤ 0.6) hexagonal double perovskite oxides have been synthesized by a solid-state reaction method by substituting Ba with Bi. The polycrystalline materials are structurally characterized by the laboratory X-ray diffraction, synchrotron X-ray, and neutron powder diffraction. The lattice parameters are found to increase with increasing Bi doping despite the smaller ionic radius of Bi3+ compared to Ba2+. The expansion is attributed to the reduction of Co/Ru-site cations. Scanning electron microscopy further shows that the grain size increases with the Bi content. All Ba2–xBixCoRuO6 (0.0 ≤ x ≤ 0.6) samples exhibit p-type behavior, and the electrical resistivity (ρ) is consistent with a small polaron hopping model. The Seebeck coefficient (S) and thermal conductivity (κ) are improved significantly with Bi doping. High values of the power factor (PF ∼ 6.64 × 10–4 W/m·K2) and figure of merit (zT ∼ 0.23) are obtained at 618 K for the x = 0.6 sample. These results show that Bi doping is an effective approach for enhancing the thermoelectric properties of hexagonal Ba2–xBixCoRuO6 perovskite oxides.