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The nature of chemisorbed CF3I and C2Cl4 on silicon surfaces has been studied using a variety of ultra-high vacuum surface-science techniques, including temperature-programmed desorption and electron-stimulated desorption. Thesticking coefficients for both CF3I and C2Cl4 on 370 K silicon surfaces are near unity. For the CF3I-Si system, SiFx species and I desorb in temperature-programmed desorption. No molecular CF3I desorbs. For the C2Cl4-Si system,SiCl2 desorbs in temperature-programmed desorption. No molecular C2Cl4 desorbs. Low-energy (