A new dirhodium(II,II) paddlewheel complex, [Rh-2(O2CC6H4COOC2H5)(4)] (1), has been synthesized using a predesigned functionalized carboxylate, namely, 4-(ethoxycarbonyl)benzoate. The target product has been crystallized from the acetone solution and structurally characterized as a bis-acetone adduct, [Rh-2(O2CC6H4COOC2H5)(4)(OCMe2)(2)]center dot C6H14 (2). By utilizing the ability of dangling ester groups to coordinate to open axial ends of neighboring dirhodium units, 1 can self-assemble to form 2D networks upon crystallization from solutions of noncoordinating solvents such as chlorobenzene and chloroform. The resulting [Rh-2(O2CC6H4COOC2H5)(4)]center dot 2C(6)H(5)Cl (3) and [Rh-2(O2CC6H4COOC2H5)(4)]center dot 2CHCl(3) (4) products have microporous solid state structures with the pores filled with the corresponding disordered solvent molecules. Notably, 3 and 4 represent unique examples of 2D extended frameworks based on dirhodium tetracarboxylate paddlewheel units devoid of any exogenous ligands. In solution, the dangling ends of carboxylate bridges of 1 have been successfully utilized for condensation reaction with the selected solid support, benzylamine-functionalized polystyrene, allowing successful heterogenization of dirhodium units through the equatorial covalent attachment to the substrate. The resulting solid product was tested as a catalyst in the cyclopropanation reaction of styrene with methyl phenyldiazoacetate to show good yields and diastereoselectivity.