Surface chemical reactions at self-assembled monolayer (SAM) films containing benzyl halide functional groups have been investigated. The benzyl halide SAM films were chemisorbed onto silicon or silicon dioxide substrates. Nucleophilic substitution at the benzyl chloride group, employing NaI, results in exchange of chlorine for iodine. The rate for surface halogen exchange was compared to the rate in solution by H-1 NMR kinetics on a model compound. The rates and yields for reactions in which the benzyl halide is converted to ethylenediamine or 3-pyridine groups were studied by UV absorption spectroscopy and X-ray photoelectron spectroscopy. The utility of the benzyl halide SAM films as surface-imaging resists and the importance of the surface modifications in a lithographic process employing ligand-based selective metalization are also discussed.