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Five new coordination polymers, {[Co-(OAc) 2 (bpe)(H 2 O)]•0.5(dmf)} n (1), {[Co(bpy) 2 (H 2 O) 4 ]-[Co(tfa)(bpy) 2 (H 2 O) 3 ](tfa) 3 •1.5(bpy)} n (2), [Co-(tfa) 2 (dps) 4 ] n (3), {[Co(tfa) 2 (bpe) 4 ]•H 2 O} n (4), and [Co-(tfa) 2 (bpp) 4 ] n (5) (where AcO − = CH 3 CO 2 − ; tfa − = CF 3 CO 2 − ; bpy = 4,4′-bipyridine; bpe = 1,2-bis(4-pyridyl)ethane; bpp = 1,3-bis(4-pyridyl)propane; dps = 4,4′-dipyridyl sulfide; dmf = N,N′-dimethylformamide) were synthesized by the reactions of Co(OAc) 2 •4H 2 O and Co(tfa) 2 •4H 2 O with different dipyridyl ligands and characterized by elemental analysis, IR spectra, and X-ray single-crystal diffraction. Compound 1 exhibits extended two-dimensional (2D) networks through the bridging AcO − and bpe ligands. The polymeric motifs in 2−5 are exclusively based on bipyridine-type ligands and results in 1D cationic chains in 2, similar charge-neutral double tapes in 3 and 4, and a 2D polymeric network in 5. In 2−5, the tfa anions coordinate to the Co(II) center in a monodentate mode. An impact of the anion's fluorination on coordination modes and supramolecular architectures is registered. Magnetic measurements reveal almost vanishing exchange interactions in the layered materials 1 and 5. The correlation of mechanical properties and crystal structure has been demonstrated for 1.