In this article, two different anionic ligands, 3,4-oxybis(benzoate) (bopH2) and sulfate, have been employed as co-ligands to perform a comparison on the structures of coordination polymers based on the Zn(II)–rigid 1,4-bis(imidazol-1-yl)benzene (bib) net. Two new coordination polymers, {Zn(bib)(bop)}∞ (1) and {Zn(bib)(SO4)}∞ (2), were synthesized from hydrothermal reactions and characterized by elemental analyses, IR and single-crystal X-ray diffraction. Complex 1 contains two unique 2-D layers, which are further interpenetrated to form a two-fold 2-D → 2-D framework. However, 2 consists of a 3-D structure with pcu topology constructed by sulfates as pillars. The structural difference of 1 and 2 indicates that size of the ancillary ligands play important roles in formation of such coordination architectures. Thermal and fluorescence properties of 1 and 2 are also investigated in the solid state. [ABSTRACT FROM AUTHOR]