Cyanido-bridged high-spin clusters revealing single-molecule magnet behavior were combined with 4,{4}'-bipyridine-N,N′-dioxide (4,{4}'-bpdo) linkers, giving unique H-bonded supramolecular (1) chains and one-dimensional coordination (2) nanowires. The hydrogen-bonded chains of 1 are embedded within the three-dimensional supramolecular network stabilized by the series of noncovalent interactions between clusters, 4,{4}'-bpdo, and solvent molecules. The coordination nanowires 2, revealing an average core diameter of about 11 \AA , are arranged parallel with the significant separation in the crystal structure, leading to a microporous supramolecular network with broad channels (12 × 12 \AA) filled by methanol and water. Both 1 and 2 are stable only in a mother solution or an organic protectant, whereas they undergo the fast exchange of methanol ligands to water molecules during drying in the air. Synthesized materials preserve the magnetic characteristics of clusters with an effective ferromagnetic coupling, giving a ground-state spin of 15/2. For 2, the additional antiferromagnetic intercluster interactions are observed. Below 3 K, the frequency-dependent (T) signals of 1 and 2 indicate the onset of slow magnetic relaxation. For 1, the relaxation time follows the Arrhenius law with an energy gap of and , which is consistent with single-molecule magnet behavior.