Two heterometallic Cu(II)/Ni(II) coordination polymers, [Cu 2 (Hbdea) 2 Ni(CN) 4 ] n (1) and [Cu 2 (dmea) 2 Ni-(CN) 4 ] n •nH 2 O ( 2), were successfully self-assembled in water by reacting Cu(II) nitrate with H 2 bdea (N-butyldiethanolamine) and Hdmea (N,N-dimethylethanolamine) in the presence of sodium hydroxide and [Ni(CN) 4 ] 2− . These new coordination polymers were investigated by single-crystal and powder X-ray diffraction and fully characterized by FT-IR spectroscopy, thermogravimetry, elemental analysis, variable-temperature magnetic susceptibility measurements, and theoretical DFT and CASSCF calculations. Despite differences in crystal systems, in both compounds, each dinuclear building block [Cu 2 (μ-aminopolyalcoholate) 2 ] 2+ is bridged by diamagnetic [Ni(CN) 4 ] 2− linkers, resulting in 1D (1) or 2D (2) metal−organic architectures. Experimental magnetic studies show that both compounds display strong antiferromagnetic coupling (J = −602.1 cm −1 for 1 and −151 cm −1 for 2) between Cu(II) ions within the dimers mediated by the μ-O-alkoxo bridges. These results are corroborated by the broken symmetry DFT studies, which also provide further insight into the electronic structures of copper dimeric units. By reporting a facile self-assembly synthetic protocol, this study can be a model to widen a still limited family of heterometallic Cu/Ni coordination polymer materials with different functional properties.