The successful introduction of azide ions as secondary bridges into the FeIII-NiII cyanide system afforded two clusters and one unique 4(3),2-ribbon chain: [(bpzpy)2Ni2(μ2-1,1-N3)2{(pzTp)Fe(CN)3}2]·3H2O [1; bpzpy = 2,6-bis(pyrazol-1-yl)pyridine, and pzTp = tetrakis(pyrazolyl)borate], [(L1)2Ni4(μ3-1,1,1-OCH3)2(μ2-1,1-N3)2(H2O)2{(Tp)Fe(CN)3}2]·2CH3OH·H2O [2; Tp = hydrotris(pyrazolyl)borate, and HL1 = 2,6-bis{(2-hydroxypropylimino)methyl}-4-methylphenol], and [(L2)2Ni3(μ2-1,1-N3)4{(pzTp)Fe(CN)3}2]n (3; L2 = 2-{[phenyl(pyridin-2-yl)methylene]amino}ethan-1-amine). Both 1 and 2 feature the centrosymmetric {FeIII-NiII2-FeIII} and {FeIII-NiII4-FeIII} rodlike structures in which the two peripheral [(TpR)Fe(CN)3]- anions act as monodentate ligands via one cyanide group to link the central azide-bridged [Ni2] and [Ni4] subunit, respectively, while 3 displays an extended structure of the double-zigzag (4,2-ribbon) chain in which the double end-on azide-bridged trinuclear [Ni3] subunits serve as the 4-connected nodes. Magnetic study revealed that intramolecular ferromagnetic coupling is dominated by the azide or cyanide bridges in all of the complexes. Remarkably, complex 1 behaves as a single-molecule magnet with an effective energy barrier of 16.5 cm-1 at zero dc field, while complex 3 exhibits metamagnetism with a hidden spin canting property below 12 K.