Self-assembled monolayers formed by thermal hydrosilylation of a trifluoroacetyl-protected alkenylthiol on Si−H surfaces, followed by removal of the protecting groups, yield essentially oxide-free monolayers suitable for the formation of Si−C₁₁H₂₂−S−Hg and Si−C₁₁H₂₂−S−Au junctions in which the alkyl chains are chemically bound to the silicon surface (via Si−C bonds) and the metal electrode (via Hg−S or Au−S bonds). Two barriers to charge transport are present in the system:  at low bias the current is temperature activated and hence limited by thermionic emission over the Schottky barrier in the silicon, whereas as at high bias transport is limited by tunneling through the organic monolayer. The thiol-terminated monolayer on oxide-free silicon provides a well-characterized system allowing a careful study of the importance of the interfacial bond to the metal electrode for current transport through saturated molecules.