Density　functional　theory　(DFT)　and　coupled　cluster　theory　(CCSD(T))　calculations　are　performed　to　investigate　the　geometric　and　electronic　structures　and　chemical　bonding　of　a　series　of　Cu-doped　zinc　oxide　clusters:　CunZn3O3　(n　=　1–4).　The　structural　evolution　of　CunZn3O3　(n　=　1–4)　clusters　may　reveal　the　aggregation　behavior　of　Cu　atoms　on　the　Zn3O3　cluster.　The　planar　seven-membered　ring　of　the　CuZn3O3　cluster　plays　an　important　role　in　the　structural　evolution;　that　is,　the　Cu　atom,　Cu　dimer　(Cu2)　and　Cu　trimer　(Cu3)　anchor　on　the　CuZn3O3　cluster.　Additionally,　it　is　found　that　CunZn3O3　clusters　become　more　stable　as　the　Cu　content　(n)　increases.　Bader　charge　analysis　points　out　that　with　the　doping　of　Cu　atoms,　the　reducibility　of　Cu　aggregation　(Cun−1)　on　the　CuZn3O3　cluster　increases.　Combined　with　the　d-band　centers　and　the　surface　electrostatic　potential　(ESP),　the　reactivity　and　the　possible　reaction　sites　of　CunZn3O3　(n　=　1–4)　clusters　are　also　illustrated.　©　2024　by　the　authors.