Time-resolved fluorescence-detected magnetic resonance (FDMR) was used to study radiolysis of organic solids at low temperatures (4-30 K). The mobility of charges generated in the primary events of solid-state radiolysis may be accounted for by two mechanisms : single-step tunneling and relatively slow (10(6)-10(7) s(-1)) resonant charge transfer involving the solvent hole. Acting together, these mechanisms engender a variety of unusual and previously unknown spectral features. Although the tunneling satisfactorily explains FDMR behavior in general, quantitative agreement is poor, particularly for donor-acceptor systems. It appears that the origin of this discrepancy lays in an underestimation of the tunneling radii in reactions of negative charges. The latter is rationalized in terms of a selectivity of FDMR toward mobile weakly bound electrons and excited radical anions formed after electron scavenging. The possible nature of these weakly bound electronic states is discussed.