The interaction of transition metal complexes Co(phen) 2 TATP 3+ , Co(phen) 3 3+ and Co(bpy) 3 3+ (where TATP ¼ 1,4,8,9-tetra-aza-trisphenylene, phen ¼ 1,10-phenanthroline, and bpy=2,2¢-bipyridine) with calf thymus DNA was investigated using the rotating ring-disk electrode technique. The values of the apparent diffusion coefficient and rate constant at the formal potential for reduction of these three polypyridyl cobalt complexes were found to decrease significantly in the presence of DNA as compared with that in the absence of DNA. The formal potentials at which the redox reaction takes place in the absence or presence of DNA were in the order of Co(phen) 2 TATP 3+/2+ > Co(phen) 3 3+/2+ > Co(bpy) 3 3+/2+ . The interaction between the complexes and DNA varied significantly, depending on the nature of ligands. The binding strength of these complexes to DNA was found in the order of Co(phen) 2 TATP 3+ > Co(phen) 3 3+ > Co(bpy) 3 3+ . The interaction modes of the polypyridyl cobalt complexes with DNA were discussed in line of electrochemical observations.