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.