To apply the laser ablation technique for decontamination of metal wastes contaminated with radioactive nuclides, the effect of irradiation atmospheres on removal of oxide layers on steel surfaces by laser ablation was studied. Based on the assumption that the absorption of laser light follows the Lambert-Beer law, ablation parameters, such as absorption length and threshold fluence for ablation, of sintered Fe2O3 and stainless and carbon steels were measured in He, O2, Kr, or SF6 atmospheres. The results indicated that SF6 was the most effective gas of all irradiation atmospheres studied for the exclusive removal of oxide layers formed on stainless and carbon steel samples in high-temperature pressurized water. Secondary ion mass spectroscopic measurement and scanning electron microscopic observation confirmed that no oxide layer existed on the steel samples after the exclusive removal with laser irradiation.