Six fluconazole-bridged cobalt(II) coordination polymers, namely [Co(HFlu) 2 (H 2 O) 2 ](ClO 4 ) 2 (1), [Co(HFlu) 2 (H 2 O)(AcO)](AcO)·2C 2 H 5 OH (2), [Co(HFlu) 2 Cl 2 ]·2C 2 H 5 OH (3), [Co 3 (Flu) 2 (acac) 4 ]·C 2 H 5 OH (4), [Co(HFlu) 2 (malo)(H 2 O)]·3H 2 O (5), and [Co(HFlu) 2 (fum)(H 2 O) 2 ]·H 2 O (6) (HFlu=2-(2′,4′-difluorophenyl)-1,3-bis(1,2,4-triazol-1-yl)-propan-2-ol, AcOH=acetate acid, Hacac=acetylacetonate, H 2 malo=malonate acid, H 2 fum=fumaric acid), have been synthesized and structurally characterized, and the thermal, fluorescent and magnetic properties investigated. The crystal structures display the one-dimensional cationic double-bridged chain consisting of 20-membered macrocycles to be parallel in 1 and perpendicular in 2. The structure of 3 consists of two-dimensional neutral rhombic grid in bc plane with (4,4) topology and alternative P/M helices intersecting at the Co sites along b direction. Complex 4 shows one-dimensional polymeric chain, in which binuclear Co 2 (Flu) 2 (acac) 2 units act as bridging blocks to link Co(acac) 2 nodes through triazolyl nitrogen atoms. The structure of 5 shows dimeric 20-membered macrometallacyclic motif. Complex 6 shows HFlu-bridged one-dimensional chain, which is stabilized by hydrogen-bonding interactions to produce alternative hydrophobic and hydrophilic architecture. Complexes 1–3 and 5–6 exhibit the similar electronic absorption and fluorescent spectra as those of HFlu, while complex 4 shows a fluorescent quenching phenomenon. Fluorescence titration of HFlu suggests that the fluorescent intensities at the maximal emission decrease upon the addition of Co(acac) 2 . The variable-temperature magnetic measurement of 4 reveals weak ferromagnetic interaction combined with the spin–orbit coupling effect in the 1-D Co(II) chain.