Ricinus communis L. is a hyperaccumulation plant newly discovered in an abandoned land of Cu mine in China. A hydroponic experiment was then carried out to determine the root exudates in the Cu-tolerant castor (Ricinus communis L.). Plants were grown in nutrient solution with increasing level of Cu doses (0, 100, 250, 500, and 750 μmol/L Cu) in the form of CuSO4. Cu accumulation in the roots and shoots of castor, and root exudates collected from the castor were measured. The results indicated that the castor had a high Cu accumulation capacity and the Cu concentrations in the shoots and roots of the castor treated with 750 μmol/L Cu were 177.1, 14586.7 mg/kg, respectively. Tartaric was the largest in the root exudates in terms of concentrations, which reached up to 329.13 μmol/g (dry plant) in the level of 750 μmol/L Cu. There was a significantly positive linear relationship between the Cu concentration in root and the concentration of succinic (R = 0.92, P < 0.05), tartaric (R = 0.96, P < 0.01), and citric (R = 0.89, P < 0.05). These results indicated that the difference in root exudation from castor could affect their Cu tolerance. What is more, significant is that the high tartaric and citric, the low oxalic and cysteine in the root exudation of castor contributed to toleration of high Cu concentrations.