Halogenated organic compounds are common pollutants in groundwater. Consequently, there is widespread interest in understanding the reactions of these compounds in the environment and developing remediation strategies. One area of ongoing research involves the reductive dechlorination of organohalides with zero-valent metals or metal sulfide minerals. These processes have been studied almost exclusively from the perspective of the aqueous phase. In this paper we illustrate the utility of surface analysis techniques, including electron spectroscopies, vibrational spectroscopies, and atomic force microscopy in elucidating the roles played by the surface. A dual analysis approach to the study of reductive dechlorination, combining traditional solution phase analysis with surface analytical techniques, also is demonstrated using a liquid cell coupled to an ultrahigh vacuum surface analysis chamber.