The chemical state, electronic properties, and geometric structure of methyl-terminated Si͑111͒ surfaces prepared using a two-step chlorination/alkylation process were investigated using high-resolution synchrotron photoelectron spectroscopy and low-energy electron diffraction methods. The electron diffraction data indicated that the methylated Si surfaces maintained a ͑1 ϫ 1͒ structure, where the dangling bonds of the silicon surface atoms were terminated by methyl groups. The surfaces were stable to annealing at 720 K. The high degree of ordering was reflected in a well-resolved vibrational fine structure of the carbon 1s photoelectron emission, with the fine structure arising from the excitation of C-H stretching vibrations having h = 0.38± 0.01 eV. The carbon-bonded surface Si atoms exhibited a well-defined x-ray photoelectron signal having a core level shift of 0.30± 0.01 eV relative to bulk Si. Electronically, the Si surface was close to the flat-band condition. The methyl termination produced a surface dipole of −0.4 eV. Surface states related to CH 3 and Si-C bonding orbitals were identified at binding energies of 7.7 and 5.4 eV, respectively. Nearly ideal passivation of Si͑111͒ surfaces can thus be achieved by methyl termination using the two-step chlorination/ alkylation process.