Two metal‐organic coordination polymers of CoII with the molecular formulae [Co(L1)(tp)(H2O)2]n (1) and [Co(L2)(tp)·H2O]n (2) [L1 = 1, 4‐bis(benzimidazole‐1‐ylmethyl)‐ benzene; L2 = 1, 1‐(1, 4‐butanediyl)bis(5, 6‐dimethylbenzimidazole); tp = terephthalate] were synthesized and characterized by single‐crystal X‐ray diffraction studies, infrared spectroscopy (IR), thermogravimetric analysis (TGA), X‐ray powder diffraction (XRPD), and elemental analysis. The structure determination of complex 1 reveals a 2D layer with (4, 4) topology, with CoII ions at the nodes connected through tp and L1 co‐ligands. Complex 2 is the first example of a four‐connected SrAl2 structure type (sra, 42638 topology) with threefold interpenetration in CoII coordination frameworks, forming by bridging L2 and tp co‐ligands. In addition, the fluorescence and catalytic performances of the complexes for the degradation of methyl orange were investigated.