Nowadays the Co(II)-based coordination networks function as effective heterogeneous and reusable catalysts [1], are discussed as prototypes of future magnetic materials [2] and effective biodegradable drug carriers [3]. Solvatochromism as the inherent property allows using them as sensors for small molecules showing guest selectivity and providing a response in the UV/Vis/NIR spectral range to the guest inclusion [4]. Five new coordination polymers, {[Co(OAc)2(bpe)(H2O)]·0.5(dmf)}n (1), {[Co(bpy)2(H2O)4][Co(Tfa)(bpy)2(H2O)3](Tfa)3·(bpy)1.5}n (2), [Co(Tfa)2(dps)4]n (3), {[Co(Tfa)2(bpe)4]·H2O}n (4), and [Co(Tfa)2(bpp)4]n (5) (where AcO– = CH3CO2 –; Tfa– = CF3CO2 –; bpy = 4,4'-bipyridine; bpe = 1,2-bis(4-pyridyl)ethane; bpp = 1,3-bis(4pyridyl)propane; dps = 4,4'-dipyridyl sulfide; dmf = N,N'-dimethylformamide) were synthetized by the reactions of Co(OAc)2·4H2O and Co(Tfa)2·4H2O with different dipyridyl ligands and characterized by elemental analysis, IR spectra, and X-ray single-crystal diffraction. The IR spectra of complexes 1–5 exhibit very strong and broad bands due to asymmetric and symmetric stretching of coordinated carboxylic groups in the 1609–1564 (νasCOO) and 1458–1411 cm–1 (νsCOO) regions for acetate anion in 1, and in the 1703–1589 and 1465–1415 cm–1 regions for trifluoroacetates in 2–5, respectively. These bands overlap with the ν(C=N) stretching vibrations of the aromatic rings of the pyridyl containing ligands. The IR spectra of 2-5 also display strong bands in the range 1203–1125 cm–1 arising from δ(C-F) asymmetric and symmetric bending vibrations of Tfa– groups. The presence of the coordinated water molecules in 1 and 2 is justified by broad signals at 3265 and 3229 cm–1, respectively. The single crystal X-ray analysis revealed the 2D polymeric networks in 1 and 5, 1D cationic chains in 2, and similar charge-neutral double tapes in 3 and 4. An impact of the anion’s fluorination on coordination modes and supramolecular architectures is registered and discussed. Magnetic measurements for the two layered structures 1 and 5 indicate that the Co(II) centers interact only very weakly. The mechanical properties for 1 reveal pronounced anisotropy of hardness with the most soft layer facet.