A new class of dirhodium(II) complexes with tethered sulfonamide and carboxamide ligands was synthesized and characterized. A new type of coordination mode was found for the quinoline moiety containing a sulfonamide ligand, which afforded the axially coordination-free bimetallic dirhodium complexes. Studies were conducted on the catalytic properties of these complexes for cyclopropanation reactions, and the findings indicate that a free axial coordination site is crucial for achieving a high degree of reactivity.