Cyanide wastewater, as a highly toxic pollutant, has detected in cyanidation factories, which is seriously harmful to the environment so that the further treatment is needed. In the present study, a simple and effective Ag-doped coralloid titanosilicate zeolite (CTS-Ag) with high adsorption and catalytic performance was developed via hydrothermal method and ion exchange method in order to investigate as a catalytic activity for the degradation of cyanide wastewater. The prepared materials were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), thermogravimetric analysis (TGA), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), N2 adsorption-desorption test and X-ray photoelectron spectroscopy (XPS). Besides these, photocatalytic performance of CTS-Ag was evaluated by photodecomposition of cyanide and generation of reactive oxygen species (ROS), and the effects of components, doping concentration, catalyst dosage, wastewater concentration and wavelength of light source were investigated. The results showed that the degradation efficiencies of total cyanide, copper and zinc could reach 98.00%, 99.41% and 98.44%, respectively. The kinetics of cyanide degradation followed the pseudo-first-order model. The degradation mechanism of cyanides was elucidated based on synergistic effect of photocatalytic oxidation and the functional Ag2O. Although the metal doped in the photocatalyst can improve its properties, the Ag2O species deposited on the surface can directly participate in the reaction with the pollutants to accelerate their enrichment and degradation thus significantly improved the degradation ability for cyanides. The photoelectric properties of CTS-Ag obviously improved the migration and separation of photo-generated electrons (e−) and holes (h+), so that high photocatalytic efficiency was obtained. XPS analysis showed that cyanide was finally degraded to COX/NOX, and the copper and zinc were removed in the form of Cu (II) and Zn (II).