An Ag(I) coordination polymer {[Ag(L)(Htbip)]}n (H2tbip = 5-tert-butylisophthalic acid, L = 1,1-(1,4- butanediyl)bis-1H-benzimidazole) is synthesized and characterized by the elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single crystal X-ray diffraction. It crystallizes in the monoclinic space group P21/c, a = 18.2755(13), b = 8.8515(6), c = 18.4000(13) Å, β = 104.9200(10)°, V = 2876.1(3) Å3, Z = 4, C30H31,AgN4O4, Mr = 619.46, Dc = 1.431 g/cm3, μ = 0.742 mm−1. The structural analyses display that this compound has a 1D zigzag chain structure which is further extended into a 3D supramolecular framework through O–H⋯O hydrogen bond interactions. The complex can be stable up to 215°C.