This study investigates the aqueous microsolvation of CdCl₂ using density functional theory (DFT) and Born-Oppenheimer molecular dynamics (BO-MD) simulations. The optimized structures and binding energies of CdCl₂-(H₂O)ₙ clusters with n ranging from 1 to 24 are computed at the B3PW91/6-31G** level. The solvation patterns obtained at the DFT level are validated at the MP2/AVTZ level for n < 6. Unlike HgCl₂, where there are at most three Hg-Oₓ orbital interactions, Cd establishes four equatorial orbital interactions with water for n > 6, leading to a planar square bipyramid hexacoordination around Cd. The first solvation shell is fully attained with 12 water molecules. The water binding energies are significantly larger for CdCl₂ compared to HgCl₂ due to stronger Cd-Oₓ interactions. For the largest system studied, CdCl₂-(H₂O)₂₄, both pentacoordinated and hexacoordinated structures are found, but BO-MD simulations at 700 K reveal the greater stability of the pentacoordinated species. The radial distribution function of Cd-O(water) shows a bimodal distribution with two maxima at 2.4 Å and 4.2 Å, indicating different coordination spheres even with a small number of solvating water molecules. The study provides insights into the aqueous solvation behavior of CdCl₂, which is crucial for understanding its transmembrane passage and potential toxicity.This study investigates the aqueous microsolvation of CdCl₂ using density functional theory (DFT) and Born-Oppenheimer molecular dynamics (BO-MD) simulations. The optimized structures and binding energies of CdCl₂-(H₂O)ₙ clusters with n ranging from 1 to 24 are computed at the B3PW91/6-31G** level. The solvation patterns obtained at the DFT level are validated at the MP2/AVTZ level for n < 6. Unlike HgCl₂, where there are at most three Hg-Oₓ orbital interactions, Cd establishes four equatorial orbital interactions with water for n > 6, leading to a planar square bipyramid hexacoordination around Cd. The first solvation shell is fully attained with 12 water molecules. The water binding energies are significantly larger for CdCl₂ compared to HgCl₂ due to stronger Cd-Oₓ interactions. For the largest system studied, CdCl₂-(H₂O)₂₄, both pentacoordinated and hexacoordinated structures are found, but BO-MD simulations at 700 K reveal the greater stability of the pentacoordinated species. The radial distribution function of Cd-O(water) shows a bimodal distribution with two maxima at 2.4 Å and 4.2 Å, indicating different coordination spheres even with a small number of solvating water molecules. The study provides insights into the aqueous solvation behavior of CdCl₂, which is crucial for understanding its transmembrane passage and potential toxicity.