Abstract: Copper in copper ores is commonly determined by a manual visual titration method. The method has large errors, poor precision and poor reliability due to the need to gauge the end of the chemical reaction by a chemical indicator. Based on these disadvantages, a high precision determination method for high Cu content in Cu ores has been developed. In this new method, the terminal point is determined by intelligent potentiometric titrator automatically and the amount of sodium thiosulfate standard solution is accurate to 0.001 mL by a high-resolution dosing device. Moreover, the amount of potassium iodide is increased to eliminate the absorption of iodine with copper iodide which was produced during titration, as the copper iodide can be dissolved by high concentrations of iodide. National standard materials such as copper concentrate, chalcopyrite and lead brass with copper content ranging from 24.2% to 59.09% are determined using this method. The relative standard deviation is lower than 0.3%(n=10). The extreme differences are 0.13%, 0.21% and 0.29%, better than manual visual titration. The proposed method improves the automation for accurate determination of ores with Cu content greater than 0.5%, especially for those with Cu content more than 10%.