Inverted (A/E) chemically induced dynamic electron polarization (CIDEP) is observed for random encounters of radical pairs such as the phenoxyl radical together with either e(aq)(-) or the radical anion of benzoate. A number of experiments have been carried out to clarify the relationship of the energetics of the reaction of oxidizing and reducing radicals to CIDEP behavior. Steady-state and time-resolved ESR experiments were carried out to determine the sense of F-pair CIDEP for a number of different radical pairs consisting of a phenoxyl radical together with one of a series of radical anions of para-substituted benzoates. Inverted polarization (A/E) was found for eaq- or the radical anions of benzoate and 4-methyl, 4-methoxy, and 4-carboxybenzoates in the presence of phenoxyl or 4-methylphenoxyl radicals. Other radical anions such as those of 4-formylbenzoate showed normal polarization. The pair consisting of e(aq)(-) with the p-benzosemiquinone radical anion also showed inverted polarization, but normal polarization was seen for all radical anions paired with the semiquinone radical anion. The corresponding excited-state energies of the reaction product (phenolate anion or hydroquinone dianion) were determined from the emission spectra, and the energies of the radical pairs were estimated from electrochemical experiments. The inverted CIDEP is clearly the result of a change in the normal energy ordering of the radical-pair states so that the triplet state is lower. The observations are discussed in terms of the electron-transfer reaction within the radical pairs using the approach presented by Kobori et al.