A new approach for studying the electronic properties of the Ⅱ-Ⅵ compounds is presented , in which the atoms in a cluster is divided into the inner ones and boundary ones, the influence of the charge transfer on the environmental potential produced by the ion lattices outside the cluster is taken into account. The occupation number of the cluster molecular orbitals is calculated by a modified DV-SCC method with a new environmental potential. The net charges and the charge transfer of the clusters TM: ZnSe are investigated from the calculated electronic structure parameters. Some of new regularity, the behaviour and concept, due to the interaction between the transition-metal ions and ligand ions are discussed in brief.