Thermal conductivity of the lowermost mantle governs the heat flow out of the core energizing planetary-scale geological processes. Yet, there are no direct experimental measurements of thermal conductivity at relevant pressure–temperature conditions of Earth's core–mantle boundary. Here we determine the radiative conductivity of post-perovskite at near core–mantle boundary conditions by optical absorption measurements in a laser-heated diamond anvil cell. Our results show that the radiative conductivity of Mg0.9Fe0.1SiO3 post-perovskite (∼1.1 W/m/K) is almost two times smaller than that of bridgmanite (∼2.0 W/m/K) at the base of the mantle. By combining this result with the present-day core–mantle heat flow and available estimations on the lattice thermal conductivity we conclude that post-perovskite is at least as abundant as bridgmanite in the lowermost mantle which has profound implications for the dynamics of the deep Earth.