Radicals formed by the addition of hydrogen (H) or muonium (Mu) to tris(8-hydroxyquinoline)alurninum(III) (Alq(3)) have been studied using density functional theory (DFT) calculations. Drew et al. (Phys. Rev. Len. 2008, 100, 116601) studied Alq3 using the longitudinal field muon spin relaxation technique and assumed the formation of muoniated radicals and rapid intermolecular electron hopping with a rate of (1.4 +/- 0.2) x 10(12) In this work, the results of DFT calculations on Alq3, the H/Mu adducts of Alq(3), and the corresponding anions and cations are reported. The energy required to transfer an electron to or from the H/Mu adducts of Alq(3) is prohibitively large, ranging from 4.09 to 5.68 eV, which suggests that the unpaired electron does not hop onto neighboring molecules and that there is no long-range diffusion of the unpaired electron. The hyperfine coupling constants for the muoniated radicals were calculated and used to predict avoided level crossing resonance fields, which will allow experimenters to confirm that the unpaired electron is localized in close proximity to the muon.