In thin film transistor‐liquid crystal display (TFT‐LCD), the copper/indium tin oxide (Cu/ITO) layer was often used to be gate line. In this event, the patterning of ITO is necessary and important. However, the high temperature generated during Cu deposition will cause ITO to crystallize, which is not conducive to ITO etching. In this paper, the ITO films prepared by radio frequency (RF) magnetron sputtering were annealed according to the monitoring results of production line to simulate and study the effect of crystallization on the etching properties of ITO film. When the annealing temperature was less than 200°C, no large size grains were detected in ITO films, and the ITO films could be easily etched by etchant. However, the ITO films transformed from amorphous structure to polycrystalline structure after being annealed more than 200°C. After wet etching experiments, the polycrystalline ITO films could be hardly removed by etchant. The X‐ray photoelectron spectroscopy (XPS) results showed that high temperature annealing induced a large amount of Sn4+ on ITO films surface. The Sn4+ was difficult to be dissolved by acid under normal conditions, which might be the most important factors that led to the greatly decreased etching rate for polycrystalline ITO films.