Two new CoII coordination polymers, [Co(L1)0.5(hip)]n (1) and [Co(L2)(mip)·2H2O]n (2) [L1 = 1,1′‐(1,4‐butanediyl)bis‐1H‐benzimidazole, L2 = 1,3‐bis(5,6‐dimethylbenzimidazol‐1‐yl)‐2‐propanol, H2hip = 5‐hydroxyisophthalic acid, H2mip = 5‐methylisophthalic acid], were synthesized under hydrothermal conditions and structurally characterized by elemental analysis, IR spectroscopy, and X‐ray single‐crystal diffraction. Complex 1 exhibits a 3D supramolecular network constructed with 2D (4,4) layer by O–H···O hydrogen bonding. Complex 2 has 1D ladder‐like chains, which are further assembled into a 3D supramolecular framework by π–π stacking interactions. In addition, fluorescence and catalytic properties of compounds 1 and 2 were investigated in solid state.