Benzophenone ((C
6H
5)
2CO) and decafluorobenzophenone ((C
6F
5)
2CO) were applied to elucidate the photochemical reaction pathway of hydrogen peroxide (H
2O
2) with dimethylsulfoxide (DMSO). When a solution of benzophenone in DMSO was excited with the 355 nm laser light, three transient
species were observed in the time-resolved electron paramagnetic resonance spectra: benzophenone ketyl (C
6H
5)
2COH
⋅, methyl
⋅CH
3, and methylsulfinic methyl
⋅CH
2SOCH
3 radicals. However, when decafluoro-benzophenone was used with DMSO, only ketyl and methylsulfinic methyl radicals were observed
under the same experimental conditions. When the reaction of benzophenone and DMSO was carried out in the presence of H
2O
2, different time profiles of
⋅CH
3 radicals were observed. In the reaction of decafluorobenzophenone-DMSO-H
2O
2, the time profiles of the radicals were not affected by the presence of H
2O
2. Thus, these results verify that
⋅CH
3 radicals are regenerated in a cyclic pathway, in which
⋅CH
3 radicals attack H
2O
2. The regeneration pathway allows us to observe f-pair polarization throughout the lifetime of
⋅CH
3 radicals, which last several microseconds, an order of magnitude longer than the
T
1 relaxation time of
⋅CH
3 radicals.