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Silibinin is a major component of silymarin (Silybum marianum), which has traditionally been used to treat a wide range of liver diseases. Recently, Silibinin and its derivatives in both in vitro and in vivo models have shown a significant inhibitory effect in different types of tumors including skin, breast, lung, colon, bladder, prostate, kidney and liver. The chemo-preventive potentials of this flavonoid are promoted by inducing apoptosis, enhancing tumor suppressor and cell cycle inhibitors, inhibiting growth factors, and attenuating proliferative mediators. In this paper, a summary of the important molecular mechanisms involved in Silibinin anti-cancer effects, animal studies and important clinical trials have been presented. The results of these studies will provide a more comprehensive perspective of Silibinin and help to optimize its effects in cancer chemotherapy.