Heterogenized Ir(III) catalysts were synthesized through the formation of coordination bonds between Ir(III) ions and heptazine-based covalent organic frameworks (COFs). The coordination environment of the Ir(III) ion contained the two heptazinyl nitrogen atoms as well as Cp* and Cl− anions. The heterogeneous catalyst exhibits high CO2 hydrogenation activity (turnover number (TON) = 6400 and turnover frequency (TOF) = 1500 h−1). In addition, the sub-micron sized catalyst was easily separated by filtration and the catalytic efficiency of the isolated catalyst was demonstrated over repeated cycles.