Two new coordination polymers, DUT-82 and DUT-83 (DUT – Dresden University of Technology), were synthesized by a solvothermal reaction in methanol of rhodium(II) acetate and the tricarboxylic acid H3btc (btc – benzene-1,3,5-tricarboxylate) or H3btb (btb – benzene-1,3,5-tribenzoate), respectively. After drying using supercritical carbon dioxide, aerogels with specific surface areas of up to 1150 m2 g−1 and pore volumes of up to 2.26 cm3 g−1 were obtained. Although there is no long range order in the materials, the presence of rhodium paddle-wheel units and thus a local order was proven by X-ray absorption spectroscopy measurements. DUT-82 shows good performance in the adsorption of hydrogen and a high affinity for carbon monoxide, which is rarely observed for metal–organic frameworks. Catalytic investigations demonstrate the activity of DUT-82 in the heterogeneous hydrogenation of styrene as a model system. DUT-82 can be recycled for at least ten cycles underlining the stability during the course of reaction.