The structures and electronic properties of Ag_nCu_(8-n) clusters were investigated in detail using density functional theory (DFT), employing the Perdew–Wang 1991 (PW91) exchange–correlation functional combined with the triple‐zeta valence correlation‐consistent basis set with pseudopotentials (cc‐pVDZ‐PP). All calculations were performed in the gas phase to obtain intrinsic structural and electronic characteristics without solvent effects. Two of the most stable geometries of the pure Ag₈ and Cu₈ clusters were considered: the tetracapped tetrahedron and the monocapped pentagonal bipyramid. A series of computational evaluations was carried out, including the determination of ionization potential, electron affinity, electronegativity, chemical hardness, electrophilicity index, average binding energy, second‐order energy difference, and the HOMO–LUMO energy gap. The results indicate that the tetracapped tetrahedron geometry is the most dominant and energetically favorable form, whereas only the Cu₈ cluster adopts the monocapped pentagonal bipyramid as its most stable configuration. When forming Ag_nCu_(8-n) bimetallic clusters, the most stable geometry consistently follows the rule that copper atoms preferentially occupy the inner positions of the cluster, while silver atoms are located on the outer shell. Natural bond orbital (NBO) analysis reveals that the frontier orbitals are strongly dominated by the d orbitals of copper atoms, influencing the clusters’ reactivity. Furthermore, electrostatic potential (ESP) mapping was performed to identify the most chemically active sites on the clusters. These findings provide valuable insights and suggest promising directions for applying silver–copper bimetallic clusters in chemical sensing, molecular adsorption, and catalytic processes for various chemical reactions.