The electrochemical reduction of a variety of halogenated aromatic compounds is studied using polarographic and voltammetric techniques and the results analyzed by means of semiempirical and ab initio calculations. In all the cases the reduction involves the cleavage of the C-halogen bond through an irreversible electrochemical process; no evidence of a stable radical anion is observed. Comparation of the potential values (E_1/2, E_p) and calculated theoretical indices indicates, however, the formation of a π radical anion following the electron uptake. Linear relationships observed between E_p and the vertical electron affinity E_ea.v suggest that the first electron uptake determines the reduction potential values. The analysis of the theoretical results and the reaction pathway strongly suggest a step mechanism for the reduction of the halogenated compounds.