Despite the popularity and versatility of transition-metal-azolium carboxylate coordination polymers, there are very few examples of group 2 complexes supported by azolium carboxylate ligands in the literature, and there are none featuring luminescent calcium azolium carboxylates. New ionic calcium coordination networks, {[Ca2(L1)2(H2O)4](Br)4·6H2O}∞ (1), {[(L3)2Ca(H2O)2]2(Br)2}∞ (3), {[(L4)2Ca(H2O)2]2(Br)2}∞ (4), and {[(L5)2Ca3(Na)(H2O)9(Cl)](Br)6·2H2O}∞ (5) along with binuclear {[Ca2(L2)2(H2O)9](Br)4·4H2O} (2), and trinuclear {[(L6)2Ca3(H2O)9](Br)6} (6) were isolated from the reaction between the corresponding azolium carboxylates and calcium carbonate in aqueous solution. 1-6 were characterized by FT-IR, NMR, TGA, UV-vis, fluorescence and single crystal X-ray diffraction techniques. Interestingly, the first tetra-cationic binuclear calcium 2 was isolated using L2H2Br2 and hexa-cationic trinuclear calcium 6 was isolated using L6H3Br3. The 3D coordination polymers 1 and 4 were derived with the help of L1H2Br2 and L4H2Br2, respectively, through Br⋯H hydrogen bonding. The 3D MOF 3 with rhomboidal channels was constructed using L3H2Br2, where the channel size is about 4.8 × 2.9 nm. 5 was isolated as a rare 1D coordination polymer. The choice of azolium carboxylates in these solids not only changes the topology of the network but also affects the chemistry exhibited by the network. Calcium azolium carboxylate assemblies 1-4 and 6 exhibit interesting solid-state photoluminescence properties, driven by azolium carboxylate ligands. Variation of the bridging chromophore produced significant effects on the fluorescence properties. 1-4 and 6 represent the first examples of luminescent calcium azolium carboxylate complexes. As can be seen in the six metal-organic assemblies presented in this report, a combination of carboxylate groups and steric hindrance affects the topology and physical properties of the resultant solids. © The Royal Society of Chemistry 2015.