Molecular Epidemiology was originally conceived as a preventive approach, providing a valuable tool for investigating risk factors for cancer in vulnerable populations. Biomarkers can be used as early indicators of risk for preventative purposes and risk assessment. The present contribution mainly refers to in utero exposures to carcinogens, since humans are especially vulnerable during fetal development. Environmental exposures in utero can increase risks for both childhood and adult cancers; their interactions with genetic and nutritional susceptibility factors may further increase risk. Thus, the early developmental period represents an important window for cancer prevention.