In the research program of some new derivatives of spin-trap DEPMPO (5-diethoxyphosphoryl-5-methyl-1-pyrroline-N-oxide) leading to various radical adducts with photogenic ESR signals, three phosphorylated pyrroline-N-oxides were studied in spin trapping. These nitrones were proved to trap a variety of free radicals to afford adducts presenting characteristic ESR signals enabling unambiguous identification of the radical species trapped. From the general patterns of the signals, the adduct geometries were determined. Two of the nitrones bore a hydroxylmethyl substituent (HM) on the pyrroline ring, either at C3 or at C4. The two diastereoisomers of nitrone 4-HMDEPMPO, whose synthesis has been already described, were separately studied. The isomer (4R*,5R*) of 4-HMDEPMPO afforded stereoselectively, with superoxide or peroxyl radicals, trans adducts versus the phosphoryl group, however, they formed two rotamer sets in chemical exchange. In comparison with DEPMPO adducts, the exchanges rates of the conformer sets of 4-HMcisDEPMPO–OOH and 4-HMcisDEPMPO–OOtBu were 9-fold or 2-fold smaller respectively. The eight-line signals of theses adducts were easily recognisable. The trapping of the same radicals with the other diastereoisomer (4S*,5R*)-4-HMDEPMPO or with (3S*,5R*)-3-HMDEPMPO, obtained via oxidation of a phosphorylated pyrroline, led to more complicated spectra owing to the formation of diastereoisomer adducts. The signal of each diastereoisomer adduct was simulated with two species in conformational exchange. In comparison with DEPMPO, the cis-C4-substitution was proved to slow by 26-fold the exchange rate between the two rotamer sets of the trans superoxide adduct versus the phosphoryl group. The trans-C3-substitution was proved to slow by 18-fold, at 223 K, the exchange rate between the two rotamer sets of the trans terbutylperoxyl adduct. The last nitrone, a bicyclic one, named MEOOPPO (6a-methyl-(6-ethoxy-5-oxa-6-oxaphospholan-6-yl)-1-pyrroline-N-oxide) was obtained directly from (4R*,5R*)-4-HMDEPMPO in basic conditions. Superoxide with the rigid MEOOPPO reacts exclusively in trans addition versus the phosphoryl group, however, the adduct obtained in aqueous buffer was not very persistent and the nitrone was partially degraded during 30 min storage. For every nitrone, the hydroxyl radical was not added stereoselectively on one ring face and some diasteroisomer adducts were obtained.