Four complexes [Ni(DMA)₂(H₂O)₄]Cl₂·2H₂O, [Ni(DMF)₂(H₂O)4]Cl2·₂H₂O, and [Ni(DMA)₆][NiCl₄], [Ni(DMF)₂(H₂O)₂Cl₂] were isolated from ternary water-organic saline systems containing nickel chloride and N, N-dimethylacetamide-water and N, N-dimethylformamide-water binary solvents. The obtained complexes were studied by X-ray structural analysis. The formation of hydrogen bonds between water molecules of the nickel ion solvate sphere, chloride ions, and non-coordinated water molecules located in the cavity of the crystal structure was detected.