Polycyclic aromatic hydrocarbons (PAH) are considered potentially carcinogenic. Substituted PAH derivatives, in contrast, may serve as anticancer agents, and as chemotherapeutics. This article presents a review of their use. Particular emphasis is placed on the synthesis of these new compounds, electrophilic substitution reactions and novel synthetic methodologies developed in our laboratory. Based on numerous reports and the data available, we believe that DNA-intercalating and membrane-interacting sites are the target for their effects.