A reduced-pressure ultraviolet (UV) photo-oxidation process is described for the removal of organic contamination from Si surfaces with concomitant growth of an ultra-thin oxide passivation layer. As in situ photo-generation of ozone (O3) from dioxygen (O2) is impractical at millitorr pressures, a 2% O3/O2 mixture from an ozone generator is fed to the surface conditioning chamber. UV/O3 surface conditioning employing simultaneous 254/185 nm UV irradiation results in essentially complete removal of carbon contamination in 180 s at 100 mTorr and 100–200°C. Kinetics studies employing cyclohexane-contaminated Si(100) surfaces suggest that carbon removal occurs via two consecutive first-order processes: initial fast photo-oxidation of adsorbed cyclohexane to readily desorbed products and slower photo-oxidation of adsorbed carbonyl intermediates to CO2 and H2O. The activation energies for both processes are 2–3 kcal/mol, consistent with the involvement of photo-generated atomic oxygen species. Self-limiting growth of an ultra-thin oxide passivation layer occurs concomitantly with carbon removal. At saturation, the oxide layer is only 3–4 Å thick, and the growth kinetics are described by a first-order Langmuirian adsorption model.