Organoantimony(V) ferrocenyl benzoates (OFBs) [p-(C 5 H 5 FeC 5 H 4 )C 6 H 4 COO] 2 SbR 3 (R = C 6 H 5 , p-CH 3 C 6 H 4 ) (3, 4) and [m-(C 5 H 5 FeC 5 H 4 )C 6 H 4 COO] 2 SbR 3 (R = p-CH 3 C 6 H 4 ) (5) were synthesized and characterized by FT-IR, 1 H and 13 C NMR, single crystal XRD and elemental analysis. The DNA interaction of the complexes (3–5) was investigated by UV–Vis spectroscopy and cyclic voltammetry (CV). The complex-DNA binding constant was found to vary in the sequence: K 2 (4.80 × 10 5 ) > K 1 (2.36 × 10 4 ) > K 3 (1.87 × 10 4 ) > K 4 (6.61 × 10 3 ) > K 5 (6.58 × 10 3 ). The shift in peak potential, current and absorption maxima of OFBs in the presence of DNA revealed that CV coupled with UV–Vis spectroscopy could provide a convenient way to characterize complex-DNA interaction mechanism, a prerequisite for the design of new anticancer agents and understanding the molecular basis of their action.