Three new hexacyanocobaltate(III) complexes, {[M2(hmpy)4Co(µ-CN)4(CN)2]∙2H2O}n (M = Cu(II) (1), Zn(II) (2) and Cd(II) (3)) were synthesized with 2-hydroxymethylpyridine (hmpy) ligand, and characterized by vibration (FT-IR and Raman) spectral, single crystal X-ray diffraction (SC-XRD) and powder X-ray diffraction (PXRD), thermal and elemental analyses techniques. The crystallographic analyses revealed that cyanide complexes 1–3 are infinite one-dimensional coordination polymers. Each M ion is coordinated by two nitrogen and two oxygen atoms from the hmpy ligands and two nitrogen atoms from the cyanide ligands, displaying a distorted octahedral coordination geometry. Similarly, each Co(III) ion is coordinated by six carbon atoms from cyanide ligands to form a distorted octahedral coordination geometry. These complexes form 3D supramolecular networks through OH···O hydrogen bonds and CH···N interactions. Additionally, structural analyses such as metal salts, pH values of the compounds obtained under different conditions were evaluated. A synthesis-structural analyses relation was made from these data.