In this work, structures and thermodynamic properties of [CuCl(3)](-) and [CuCl(4)](2-) hydrates in aqueous solution were investigated using density functional theory and ab initio methods. Contact ion pair (CIP) and solvent-shared ion pair (SSIP) structures were both taken into account. Our calculations suggest that [CuCl(3)(H(2)O)(n)](-) clusters might favor a four-coordinated CIP structure with a water molecule coordinating with the copper atom in the equatorial position for n = 3 and 4 in aqueous solution, whereas the four-coordinated SSIP structure with one chloride atom dissociated becomes more stable as n increases to 5. For the [CuCl(4)](2-) cluster, the four-coordinated tetrahedron structure is more stable than the square-planar one, whereas for [CuCl(4)(H(2)O)(n)](2-) (n ≥ 1) clusters, it seems that four-coordinated SSIP structures are slightly more favorable than CIP structures. Our calculations suggest that Cu(2+) perhaps prefers a coordination number of 4 in CuCl(2) aqueous solution with high Cl(-) concentrations. In addition, natural bond orbital (NBO) calculations suggest that there is obvious charge transfer (CT) between copper and chloride atoms in [CuCl(x)](2-x) (x = 1-4) clusters. However, compared with that in the [CuCl(2)](0) cluster, the CT between the copper and chloride atoms in [CuCl(3)](-) and [CuCl(4)](2-) clusters becomes negligible as the number of attached redundant Cl(-) ions increases. This implies that the coordination ability of Cl(-) is greatly weakened for [CuCl(3)](-) and [CuCl(4)](2-) clusters. Electronic absorption spectra of these different hydrates were obtained using long-range-corrected time-dependent density functional theory. The calculated electronic transition bands of the four-coordinated CIP conformer of [CuCl(3)(H(2)O)(n)](-) for n = 3 and 4 are coincident with the absorption of [CuCl(3)](-)(aq) species (∼284 and 384 nm) resolved from UV spectra obtained in CuCl(2) (ca. 10(-4) mol·kg(-1)) + LiCl (>10 mol·kg(-1)) solutions, whereas the calculated bands of [CuCl(3)(H(2)O)(n)](-) in their most stable configurations are not when n = 0 - 2 or n > 4, which means that the species [CuCl(3)](-)(aq) exists in those CuCl(2) aqueous solutions in which the water activity is neither too low nor too high. The calculated bands of [CuCl(4)(H(2)O)(n)](2-) clusters correspond to the absorption spectra (∼270 and 370 nm) derived from UV measurements only when n = 0, which suggests that [CuCl(4)](2-)(aq) species probably exist in environments in which the water activity is quite low.