The non-covalent binding of [(en)Pt(μ-dpzm) 2Pt(en)] 4+ to segments of DNA containing only G and C bases has been studied to gain an understanding of the pre-covalent binding association of cationic polynuclear platinum(II) anti-cancer drugs at G/C sites. 1H-NMR and CD spectroscopy were used to study the binding of the metal complex to the oligonucleotide d(GC) 5 and the polynucleotide poly(dG-dC)·poly(dG-dC), respectively. NOE contacts between the metal complex protons and the oligonucleotide sugar H1′ protons observed in NOESY spectra indicated that the metal complex bound in the minor groove at the central C 4 to G 7 region of the oligonucleotide. This result indicates that even though cationic polynuclear platinum(II) complexes bind covalently in the major groove at G/C sites, the pre-covalent binding association is favoured in the minor groove. CD spectra indicated that the addition of the metal complex to poly(dG-dC)·poly(dG-dC) induced some conformational changes, but it was not possible to conclude that [(en)Pt(μ-dpzm) 2Pt(en)] 4+ induced a B- to Z-type DNA transition. In addition, in vitro transcription assays using the lac UV5 promoter showed that the non-covalent binding of [(en)Pt(μ-dpzm) 2Pt(en)] 4+ was sufficiently stable to inhibit transcription, and at particular sites.