Hydrogen-terminated, chlorine-terminated, and alkyl-terminated crystalline Si(I 11) surfaces have been characterized using high-resolution, soft X-ray photoelectron spectroscopy from a synchrotron radiation source. The H-terminated Si(111) surface displayed a Si 2P(3/2) peak at a binding energy 0.15 eV higher than the bulk Si 2p(3/2) peak. The integrated area of this shifted peak corresponded to one equivalent monolayer, consistent with the assignment of this peak to surficial Si-H moieties. Chlorinated Si surfaces prepared by exposure of H-terminated Si to PCl5 in chlorobenzene exhibited a Si 2p(3/2) peak at a binding energy of 0.83 eV above the bulk Si peak. This higher-binding-energy peak was assigned to Si-Cl species and had an integrated area corresponding to 0.99 of an equivalent monolayer on the Si(I 11) surface. Little dichloride and no trichloride Si 2p signals were detected on these surfaces. Silicon(111) surfaces alkylated with CnH2n+1- (n = 1 or 2) or C6H5CH2- groups were prepared by exposing the Cl-terminated Si surface to an alkylmagnesium halide reagent. Methyl-terminated Si(I 11) surfaces prepared in this fashion exhibited a Si 2P(3/2) signal at a binding energy of 0.34 eV above the bulk Si 2P(3/2) peak, with an area corresponding to 0.85 of a Si(111) monolayer. Ethyl- and C6H5CH2 -terminated Si(111) surfaces showed no evidence of either residual Cl or oxidized Si and exhibited a Si 2P(3/2) peak similar to0.20 eV higher in energy than the bulk Si 2P(3/2) peak. This feature had an integrated area of similar to1 monolayer. This positively shifted Si 2P(3/2) peak is consistent with the presence of Si-C and Si-H surface functionalities on such surfaces. The SXPS data indicate that functionalization by the two-step chlorination/alkylation process proceeds cleanly to produce oxide-free Si surfaces terminated with the chosen alkyl group.