Recently, a novel electron spin resonance (ESR) spin-trapping agent, 2-(diphenylphosphinoyl)-2-methyl-3,4-dihydro-2H-pyrrole N-oxide (Diphenyl-PMPO), was synthesized. Because it had some advantages in stability and reactivity over conventional spin-trapping agents, we applied it to the ESR analyses of superoxide anion radical scavenging activity (SOSA) of superoxide dismutase (SOD) and of well-known natural antioxidants (green tea, oolong tea, and red wine). At the same time, the results with Diphenyl-PMPO were compared with 5,5-dimethyl-1-pyrroline N-oxide (DMPO). Our results revealed that Diphenyl-PMPO showed higher detectability than DMPO in the SOSA assays of SOD and natural antioxidants, so it could be available for the ESR analyses as an alternative to conventional spin-trapping agents.