Two new double complexes [Ni(bpy)3][Fe(CN)5(NO)]3H2O (1) and [Ni(en)2Fe(CN)5(NO)]H2O (2) have been isolated from the reactions of the mixture of NiCl2·6H2O and Na2[Fe(CN)5(NO)] in water, with bipyridine (bpy) and ethylenediammine (en) in ethanol, respectively, and have been characterized by X-ray analysis, IR, EPR, Mössbauer spectroscopy and magnetic measurements. Crystallographic data for 1 and 2 areas follows: triclinic, Full-size image (<1 K); 2: triclinic, Full-size image (<1 K). The bond angles of FeNO are nearly linear for 1 (178.3(4)°) and 2 (1i79.4(3)°). The structure of 1 consists of a double complex of a cation [Ni(bpy)3]2+ and an anion [Fe(CN)5(NO)]2−. The structure of 2 consists of a one-dimensional polymeric chain Ni(en)2NCFe(CN)3(NO)CNNi(en)2 in which the Ni(II) and Fe(II) centers are linked by two CN groups. Crymagnetic investigations (4–900 K) reveal a paramagnetic behavior for 1 and the presence of a one-dimensional Heisenberg weak antiferromagnetic chain with J=−0.47 cm−1 for 2. EPR spectra observed at ambient temperature for the Ni(II) ions in both complexes are also reported.