Five new nuclear coordination complexes based on a 2-hydroxymethylpyridine (Hhmp) ligand, [Cu4(hmp)4(CHOO)2(H2O)2](ClO4)2·2H2O (1), [Cu8(hmp)8(CHOO)4(CH3CN)2(H2O)4](ClO4)4·2CH3CN (2), {[Cu2(hmp)2(CHOO)(H2O)]ClO4·H2O}n(3), [Co9(hmp)6(CHOO)6(CO3)2(H2O)6](ClO4)2·11H2O (4), and [Co9(hmp)6(CHOO)7(CO3)2(H2O)5]ClO4·CH3CN·12H2O (5), have been synthesized through evaporation at room temperature. As expected, by changing the ratio of the mixed solvent complexes, 1–3successfully grow from a [Cu4O4] monocubane (1) to octanuclear double-cubane (2), which then further extends into polycubane (3, one-dimensional chain) via bridging ligands of formate. By changing the metal source, complexes 4and 5with a similar {Co9} cluster are successfully obtained. One water molecule coordinated with CoIIin one [Co4O4] core of complex 4has been replaced by a formate anion in complex 5, resulting in the {Co9} cluster with +2 and +1 charges, respectively. The change of charges on the clusters results in different cluster alignments, changing the intermolecular interactions in 4and 5. Magnetic measurements show that antiferromagnetism interaction changes into weak ferromagnetic interaction in complexes 1–3, while the antiferromagnetic behavior turns to glass spin in complexes 4and 5.