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The binding mode of Eu(phen) 33+ with DNA is studied by fluorescence and voltammetric methods. From theScatchard graph and the fluorescence quenching phenomenon, it is concluded that the mode of interaction betweenEu(phen) 33+ and DNA is intercalation bind by inserting the phen π-π conjugate surface between the base pairs of theDNA duplex. Voltammetry was used to confirm the results obtained from the fluorescence method, the result from bothmethods agrees with each other. The binding constant (K) and the binding site size (ns) were calculated from voltammetricdata such as the shifts in potential and limiting currents in the process of adding DNA, according to the positive shifts ofpeak potential. It was considered that the complex of the +2 ion interacted more favorably with the nucleotide bases thanthat of the +3 ion by hydrophobic interaction.