Sodium chloride (NaCl) films were grown on an Si(100)-(2 × 1) surface at near room temperature by molecular beam epitaxy (MBE). The atomic structure and growth mode of the prototypical ionic materials on the covalent bonded semiconductor surface is examined by synchrotron core-level x-ray photoemission spectrum (XPS), scanning tunneling microscopy (STM), and first-principles calculations. The Si 2p, Na 2p, and Cl 2p core-level spectra together indicate that adsorbed NaCl molecules at submonolayer coverage [i.e., below 0.4 monolayer (ML)] partially dissociate and form Si-Cl species, and that a significant portion of the dangling-bond characteristics of the clean surface remains after NaCl deposition of 1.8 MLs. The deposition of 0.65-ML NaCl forms a partially ordered adlayer, which includes NaCl networks, Si-Cl species, adsorbed Na species, and isolated dangling bonds. The STM results revealed that the first adlayer consists of bright protrusions which form small c(2 × 4) and (2 × 2) patches. Above 0.65 ML, the two-dimensional NaCl double-layer growth proceeds on top of the first adlayer.