Superoxide radical (O
2
−) was both electrochemically generated and detected at room temperature. In situ ESR spectroelectrochemistry with spin trapping was used for the radical detection. That is, the O
2
− radical was obtained in a DMSO solution under cyclic voltammetry conditions as soon as the potential of the dioxygen electroreduction was reached. This radical reacted then with a 5,5-dimethyl-1-pyrroline-
N-oxide (DMPO) spin-trap reagent present in solution to form the DMPO–
![]()
OOH adduct. The hyperfine coupling constants determined for the adduct were
aN = 1.285 mT,
![]()
and
![]()
in accord to those reported in literature.