Abstract The synthesis of Nickel[II], Cobalt[II] and Copper[II] complexes is reported. The structure of the complexes has been characterized by IR, thermal analysis and X‐ray power diffraction analysis. Electrochemical behavior of the complexes is also investigated. It is proposed that the structure of the complexes is square‐planar which can be used to explore the interaction between the complexes and DNA. Keywords: synthesischaracterizationelectrochemistryhexaaza macrocycleDNA Acknowledgments Thanks to the support of Guangxi Natural Science Funds (0302452) and Guilin Science Funds (20040104–4).