This research is mainly focused on the evaluation of TiO2/Fe2O3 composite and two industrial types of waste (kaolin (Clay-K) and a blast furnace sludge (BFS)) as adsorbent materials of cyanide and as photocatalysts. First, adsorption tests were performed in the absence of light. During photodegradation experiments, the effect of the type of irradiation (ultraviolet (UV) light), visible light and natural sunlight), irradiation time, the type of photocatalyst, as well as irradiance in case of natural sunlight use, were investigated. Adsorption results indicate that Clay-K and TiO2/Fe2O3 materials adsorb approximately twice as much cyanide compared to the BFS sample, which only adsorbs 33.3% (124.87 mg/g); this is due to its smaller specific surface area (5.69 m2/g) compared to that of the other two materials (Clay-K and TiO2/Fe2O3 (14.93 m2/g and 66.59 m2/g, respectively). The results obtained from the study of photodegradation of cyanide under UV irradiation, indicate that Clay-K and BFS samples photodegrade cyanide by 96.44% and 92.66%, respectively. On the other hand, using UV irradiation plus solar irradiation and visible plus solar irradiation, the best photocatalyst was the TiO2/Fe2O3, with 98.66% photodegradation. The use of natural sunlight (irradiance of 600 to 800 W/m2) of a NaCN solution of 750 mg/L, the BFS material was the most efficient to photodegrade cyanide, obtaining 97% in two hours and 87% in just 30 minutes of irradiation.