Two novel coordination polymers, [Bi2(2,3pydc)2(2,3pydcH)2(H2O)]n (1) and {(Et3NH)2[Bi(2,3pydc)(2,3pydcH)Cl2]}n (2) were prepared using as a prolinker pyridine-2,3-dicarboxylic acid (2,3pydcH2). The obtained complexes were fully characterized by elemental analysis, TG/DTG, FT-IR, solid-state photoluminescence, DFT calculations and single-crystal X-ray diffraction. The obtained complexes crystallized in the triclinic P-1 space group (1) and comprise dimeric units with two crystallographically different Bi(III) centers (polyhedra: distorted pentagonal bipyramid and bicapped trigonal prism) and monoclinic P21/c space group (2) with a distorted monocapped pentagonal bipyramid of Bi(III) center. The various coordination modes of bridging carboxylate ligands are responsible for the formation of 1D chains with 4,5C10 (1) and 2C1 (2) topology. The photoluminescence quantum yield for polymer 2 is 8.36%, which makes it a good candidate for more specific studies towards Bi-based fluorescent materials. Moreover, it was detected that polymer 1 is more than twice as active against H. pylori as polymer 2. It can be concluded that there is an existing relationship between the structure and the antibacterial activity because the presence of chloride and triethylammonium ions in the structure of complex 2 reduces the antibacterial activity.