A combination of experimental methods has been employed for the study of Cl2 adsorption and reaction on Si(100)–(2×1). At 100 K, Cl2 adsorption occurs rapidly to a coverage of ∼0.7 Cl/Si. This is followed by slower adsorption kinetics with further Cl2 exposure. Two Cl adsorption states are observed experimentally. One of the adsorption states is terminally bonded Cl on the inclined dangling bond of the symmetric Si2 dimer sites, with a vibrational frequency, ν(SiCl) of 550∼600 cm−1. These bonded Cl atoms give four off-normal Cl+ ESDIAD emission beams from the orthogonal domains of silicon dimer sites. The Si–Cl bond angle for this adsorption configuration is estimated to be inclined 25°±4° off-normal. The second Cl adsorption state, a minority species, is bridge bonded Cl with ν(Si2Cl) of ∼295 cm−1 which produces Cl+ ion emission along the surface normal direction. Both adsorption states are present at low temperatures. Irreversible conversion from bridge bonded Cl to terminally bonded Cl begins to occur near 300 K; the conversion is complete near ∼673 K. LEED studies indicate that the (2×1) reconstruction for the substrate is preserved for all Cl coverages. The most probable Cl+ kinetic energy in electron stimulated desorption, ESD, is 1.1−+0.30.6 eV. A significant adsorbate-adsorbate quenching effect reducing the Cl+ ion yield in ESD occurs above a Cl(a) coverage of ∼0.5 ML (monolayer) due to interadsorbate interactions. The maximum Cl+ yield is about 4×10−7 Cl+/e at an electron energy of 120 eV. Temperature programmed desorption results show that SiCl2 is the major etching product which desorbs at about 840 K.