Three unique Zn II /4-sulfobenzoate complexes based on 2,2′-bipyridine and/or 4,4′-bipyridine, [Zn(4-sb)(2,2′-bipy)(H 2 O) 3 ]·H 2 O (1), {[Zn(4,4′-bipy)(H 2 O) 4 ]·(4-sb)} n (2), and {[Zn(4-sb)(2,2′-bipy)(4,4′-bipy) 0.5 (H 2 O)]·2H 2 O} n (3) [4-sb=4-sulfobenzoate; 4,4′-bipy=4,4′-bipyridine; 2,2′-bipy=2,2′-bipyridine], have been prepared and characterized by single-crystal X-ray analyses, elemental analyses, IR, thermogravimetric analyses and fluorescent spectra. The molecular structure of the complex 1 is a monomer species, while the structures of complexes 2 and 3 are 1-D chains. The complex 2 is a cation–anion species. These extended hydrogen-bonding networks are 3-D architectures. In complexes 1 and 3 there are strong π…π stacking effects, while in complex 2 there is no such interaction. The thermal stability of complexes 1, 2, and 3 has the order of 2>1>3.