Four cyanide-bridged bimetallic Ni(II)–Fe(III) complexes have been synthesized and characterized in order to find new molecular materials with interesting magnetic properties. One-dimensional complexes of pentacyanoferrite(III), [Ni(2,3,2-tet)Fe(Him)(CN) 5 ]·3H 2 O (1), [Ni(3,2,3-tet)][Fe(CN) 5 (Him)]·2H 2 O (2), [Ni(3,2,3-tet)][Fe(CN) 5 (1-CH 3 im)]·4H 2 O (3), and [NiL 1 ][Fe(CN) 5 (1-CH 3 im)]·3H 2 O (4) have been prepared and characterized by X-ray single-crystal structure analysis and magnetic measurements. All complexes possesses linear or zigzag chains of alternate [Ni(L′)] 2+ and [Fe(L)(CN) 5 ] 2− units, which are linked by two trans/cis cyanide ligands of [Fe(L)(CN) 5 ] 2− . Magnetic studies reveal that they exhibit intermetallic ferromagnetic coupling and long-range antiferromagnetic ordering. The strength of the Ni(II)–Fe(III) magnetic coupling has been analyzed by comparison with the related cyanide-bridged Ni(II)–Fe(III) complexes.