The interaction of cobalt chloride with the non-steroidal anti-inflammatory drug indomethacin (Hindo) led to the formation of the polymeric complex [Co(indo-O)
2
(H
2
O)
2
(μ-Cl)]
n
·n(MeOH·H
2
O) bearing one chlorido bridge between the cobalt atoms. The presence of the nitrogen-donor co-ligands 2,2′-bipyridine (bipy), 2,2′-bipyridylamine (bipyam), 1,10-phenanthroline (phen) or 1
H
-imidazole (Himi) resulted in the isolation of complexes [Co
2
(μ-indo-O,O′)
2
(indo-O)
2
(bipy)
2
(μ-H
2
O)]·3.3MeOH, [Co(indo-O,O′)
2
(bipyam)]·0.9MeOH·0.2H
2
O, [Co(indo-O,O′)
2
(phen)] (
4
) and [Co(indo-O)
2
(Himi)
2
] (
5
), respectively, where the indomethacin ligands were coordinated in diverse manners. The study of the affinity of the complexes for calf-thymus DNA revealed their intercalation between the DNA-bases. The binding of the complexes to albumins was also examined and the corresponding binding constants and binding subdomain were determined. The free radical scavenging activity of the compounds was evaluated towards 1,1-diphenyl-picrylhydrazyl and 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid). Molecular modeling calculations may usually provide a molecular basis for the understanding of both the impairment of DNA by its binding with the studied complexes and the ability of these compounds to transportation through serum albumin proteins. This study can provide information for the elucidation of the mechanism of action of the compounds in a molecular level.