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Compounds from various vegetables, particularly Cruciferous family including isothiocyanates show a wide variety of cytoprotection and cancer chemoprevention. Epidemiological studies have demonstrated an association of reduced cancer risk and amount of consumption of vegetables. Glucosinolates from cruciferous vegetables have to be hydrolyzed to release isothiocyanates, importantly, phenethylisothiocyanate (PEITC). PEITC is well absorbed and metabolized by glutathione conjugation and excreted rapidly within 24 h with peak plasma concentration in man on the range of micromolar. PEITC kills various cancer cells including cancer of the bile duct with mechanisms by damaging mitochondria probably involving with translocation of Bcl2 family proteins to mitochondrial membrane and by activation of mitogen-activated protein kinase (MAPKs) pathways. The action may also be involved with an arrest of the cell cycle by inhibition of cyclin proteins. PEITC induces oxidative stress and this may potentiate the mitochondria dysfunction leading to apoptotic cell killing. Natural compounds from cruciferous family including PEITC possess a high potential of cancer prevention.