Cyclic voltammetry and controlled-potential electrolysis have been employed to investigate the reduction of some mono-, di-, tri-, and tetrahalopyrimidines at mercury cathodes in acetonitrile containing tetramethylammonium tetrafluoroborate. Two irreversible cyclic voltammetric waves are observed for reduction of 2-bromo-, 5-bromo-, and 2-chloropyrimidine; the first wave is due to cleavage of the carbon-halogen bond, and the second wave is attributable to reduction of pyrimidine. Cyclic voltammograms for 2,4-dichloro- and 4,6-dichloropyrimidine exhibit three cathodic waves, whereas that for 2,4,6-trichloropyrimidine shows four cathodic waves, arising from sequential cleavage of carbon-chlorine bonds as well as the reduction of pyrimidine. For the reduction of 2,4,5,6-tetrachloropyrimidine, a cyclic voltammogram exhibits four major irreversible cathodic waves corresponding to the cleavage of carbon-chlorine bonds, but the wave for reduction of pyrimidine is poorly defined. Bulk electrolyses of halopyrimidines at potentials for different stages of reduction lead to products that are consistent with expectations based upon cyclic voltammetry. In addition, our findings agree well with theoretical calculations of the relative stabilities of the various reduction intermediates. Mechanistic aspects of the reduction of halopyrimidines are discussed and, using homogeneous redox catalysis, we have determined the lifetimes of the electrogenerated radical-anions of 2-bromo- and 2-chloropyrimidine.