The decomposition and detoxification of compounds are of great interest in environmental protection and defense-related areas. We report the generation of gaseous excited species by scanning atmospheric radio frequency (rf) plasma and their reactions with two representative organophosphorus nerve agents, paraoxon and parathion, deposited on solid surfaces. The excited gaseous species generated in the Ar and Ar/O-2 plasma were identified as atomic oxygen, OH radical, and excited nitrogen molecule from optical emission spectroscopy analysis. The reaction of these species with paraoxon and parathion was monitored with reflection-absorption infrared spectroscopy and compared with the decomposition by UV irradiation and UV/ozone treatments. The decomposition products of the atmospheric rf plasma treatment were similar to those of the UV/ozone treatment. The atomic oxygen and excited OH species generated by the plasma appear to be responsible for the oxidation of paraoxon and parathion. The plasma-induced decomposition process was much faster and more efficient than the UV/ozone process. The complete detoxification of paraoxon and parathion upon a short time exposure to the Ar/O-2 plasma was confirmed by the Drosophila melanogaster culture test.