We report the synthesis of Rh–Sb complexes using high valent Sb ligands, Q₃SbCl₂ (1, Q = 8-quinolinyl) and Q₃SbF₂ (2), from the low valent Rh precursor [(CO)₂Rh(μ-Cl)]₂ to afford the complexes [(κ⁴-Q₃SbCl)Rh(CO)Cl][(CO)₂RhCl₂] (3) and (κ⁴-Q₃SbF₂)Rh(CO)Cl (4), respectively. The reaction of 1 with [(CO)₂Rh(μ-Cl)]₂ results in the transfer of chloride from Sb to Rh to give the ion pair 3 with a Rh–Sb bond for the cation that, according to computational analysis, has some covalent character. Replacing Sb–Cl with Sb–F bonds (i.e., compound 2) inhibited halide transfer and allowed formation of 4 with a Rh→Sb interaction that has more Z-type character than the Rh–Sb bond for complex 3. Molecular orbital and localized orbital bonding analyses are consistent with the proposed Rh→Sb interaction of 4 being more Z-type in character.