In this paper, two benzimidazole derivative ligands were obtained usingo-phenylenediamine and n-pyridine formaldehyde (n = 3, 4) by amine–aldol condensation reactions, which were reacted with selected inorganic metal salts by ambient temperature volatilization method to give compounds1–4: {[(L1)6]·[Cu8I8]}(1), {[L1]·[CuBr]·H2O}(2), {[L2]·[CuBr]}n(3), and {[(L2)4]·[Cu4I4]}(4). They were characterized by IR, UV-Vis absorption spectroscopy, thermogravimetric analysis, and single crystal X-ray analysis. Simultaneously, compounds1–4were found to possess photocatalytic degradation of ciprofloxacin (CIP) by preliminary experimental investigations.