The reactivity of nitroxyl free radicals, 4-hydroxyl-2,2,6,6-tetramethylpiperidine- N -oxyl (TEMPOL) and 3-carbamoyl-2,2,5,5-tetramethylpyrrolidine- N -oxyl (CmP), with reactive oxygen species (ROS) were compared as typical 6-membered and 5-membered ring nitroxyl compounds, respectively. The reactivity of the hydroxylamine forms of both these nitroxyl radicals (TEMPOL-H and CmP-H) was also assessed. Two free radical species of ROS, hydroxyl radical (^•OH) and superoxide (O₂^•−), were subjected to a competing reaction. ^•OH was generated by UV irradiation from an aqueous H₂O₂ solution (H₂O₂-UV system), and O₂^•− was generated by a reaction between hypoxanthine and xanthine oxidase (HX-XO system). ^•OH and O₂^•− generated by the H₂O₂-UV and HX-XO systems, respectively, were measured by electron paramagnetic resonance (EPR) spin-trapping, and the amount of spin adducts generated by each system was adjusted to be equal. The time courses of the one-electron oxidation of TEMPOL, CmP, TEMPOL-H, and CmP-H in each ROS generation system were compared. A greater amount of TEMPOL was oxidized in the HX-XO system compared with the H₂O₂-UV system, whereas the reverse was observed for CmP. Although the hydroxylamine forms of the tested nitroxyl radicals were oxidized evenly in the H₂O₂-UV and HX-XO systems, the amount of oxidized CmP-H was approximately 3 times greater compared with TEMPOL-H.