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CunOm+(n = 0 - 9, m=0- 4) cluster ions are produced by direct laser ablation of copper oxide solid. For the first time, mixed cluster ions [Na(Cu,O)n]+, [K(Cu2O)n+ (n = 1, 2) are observed with time-of-flight mass spectrometry (TOF-MS) detection. The experiments demonstrate that the channel induced by laser in the solid surface benefits the production of cluster ions, while high laser power functions oppositely, and that the observed cluster ions are produced by gas-phase ion-molecular condensation reaction.