A two-step procedure, involving radical-initiated chlorination of the Si surface with PCl5 followed by reaction of the chlorinated surface with alkyl-Grignard or alkyl-lithium reagents, has been developed to functionalize crystalline (1 1 1)-oriented H-terminated Si surfaces. The surface chemistry that accompanies these reaction steps has been investigated using X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), temperature programmed desorption spectroscopy (TPDS), high-resolution electron energy loss spectroscopy (HREELS), infrared (IR) spectroscopy in both glancing transmission (TIR) and attenuated total multiple internal reflection (ATR) modes, ellipsometry, and contact angle goniometry. The XPS data show the appearance of the Cl signal after exposure to PCl5 and show its removal, and concomitant appearance of a C Is signal, after the alkylation step. Auger electron spectra, in combination with TPD spectroscopy, demonstrate the presence of Cl after the chlorination process and its subsequent loss after thermal desorption of Si-Cl fragments due to heating the Si surface to 1200 K. High-resolution XP spectra of the Si 2p region show a peak corresponding to Si-Cl bond formation after the chlorination step, and show the subsequent disappearance of this peak after the alkylation step. IR spectra show the loss of the perpendicularly polarized silicon monohydride (Si-H) vibration at 2083 cm(-1) after the chlorination step, whereas HREELS data show the appearance of vibrations due to Si-Cl stretches upon chlorination of the Si surface. The HREELS data furthermore show the disappearance of the Si-Cl stretch and the appearance of a Si-C vibration at 650 cm(-1) after alkylation of the Si surface. Ellipsometric measurements indicate that the thickness of the alkyl overlayer varies monotonically with the length of the alkyl group used in the reactant. Contact angle and IR measurements indicate that the packing of alkyl groups in the monolayers produced by this method is less dense than that found in alkylthiol monolayers on Au. As determined by XPS, the alkylated surfaces show enhanced resistance to oxidation by various wet chemical treatments, compared to the H-terminated Si surface. The two-step reaction sequence thus provides a simple approach to functionalization of (1 1 1)-oriented, H-terminated silicon surfaces using wet chemical methods.