An innovate craft of NaOH melting-acid leaching processing was investigated for recovery of iron from a copper flotation tailings. This tailing was of a hazardous industrial waste, which contained 51.34% Fe and high content of S, Cu, Pb, Zn. The results demonstrated that iron can be increased to 62.15% with an iron recovery of Fe 87.64% under the optimal conditions (a melting temperature of 200 degrees C, a melting time of 90 min, a NaOH concentration of 1.5 mol/L and a HCl concentration of 10%), meanwhile, the content of S, Cu, Pb, Zn can be decreased to 0.12%, 0.15%, 0.17% and 0.12% respectively in the final iron concentrate. This craft can be used to utilize copper flotation tailings and produce qualified concentrate as iron-bearing feed for steel industry, which will help to solve the pollution of tailings and extend raw material sourcing for Chinese steel industry.