Tetrahydrofuran (THF) solutions of corannulene (Cor) reduced by lithium metal exhibit electron paramagnetic resonance (EPR) features that depend on the reduction stage of Cor, the temperature, and the nuclear spin (isotope effect). Photoexcitation of these solutions results in EPR emissive spectra, attributed to the trianion, Cor(3.-), and to the photoelectron, e(photo)(-). These electron spin polarized (ESP) effects are discussed within the framework of intramolecular electron transfer reactions of ion complexes of highly charged constituents, in conjunction with ESP mechanisms that take into account radical-triplet interactions.