Abstract: The work in this paper is one of the attempts to obtain more structural information from powder or frozen solution samples. The copper (Ⅱ) complexes with nitrogen as donor atoms in the form of N₄, cis N₂O₂, trans-N₂O₂ and NO₃ donor sets on the equatorial plane is treated. In this paper we will show that the magnitudes of the nitrogen hypcrfine couplings have some correlation with the donor sets as well as types of nitrogens, and the found correlation is useful for estimation or confirmation of coordination structure of copper (Ⅱ) complexes with unknown or uncertain structure.