An efficient fluorescence-enhanced probe was developed for detecting cyanide ions (CN⁻) based on a tetraphenylethene coordinated copper-iodide complex (named CIT-Z). The coordination polymers (CPs) prepared were (Z)-1,2-diphenyl-1,2-bis[4-(pyridin-3-ylmethoxy)phenyl]ethene (1Z) and a CuI cluster, where the tetraphenylethylene (TPE) pyridine derivatives acted as organic ligands and the CuI cluster acted as a metal center. The higher-dimensional CIT-Z exhibited a 3-fold-interpenetrating network structure with excellent optical properties and chemical stability. This study also provides insights into the mechanism behind the fluorescence enhancement, which is attributed to the competitive coordination between CN⁻ and the ligands. The probe showed high selectivity and sensitivity towards CN⁻, with a detection limit of 0.1 μM and good recovery in the real water samples.