The reactions of α-hydroxyalkyl radicals in aqueous medium are of interest because they exhibit a rich variety of fundamentally important competing mechanisms, such as proton-coupled electron transfer (PCET), hydrogen atom transfer, free radical substitutions, abstractions and additions, etc. We present a theoretical study of the mechanism and kinetics of the aqueous reactions of α-hydroxyisopropyl (2-propanol) radical with four halogenated organic substrates: iodoacetate (IAc), iodoacetamide (IAm), 5-bromouracil (5-BrU), and carbon tetrachloride (CCl4). The reactions are studied using density functional theory (DFT) (M06-2X), and the solvent is modeled as a polarizable continuum, either without the explicit solvent molecules or with one added water molecule. For an additional refinement, the double hybrid DFT B2PLYP energies were calculated at the M06-2X stationary points. Within this framework, for each substrate, we determine the most favorable radical-induced decomposition pathway among the several found and compare the thermochemical predictions against the experimental kinetics. The following dominant decomposition mechanisms are inferred: PCET for IAc, PCET-H2O and the I-atom abstraction for IAm, the ortho-addition to the double bond for 5-BrU, and the Cl-atom abstraction for CCl4. These pathways are invariably characterized by the negative apparent activation energies. Whereas for 5-BrU and CCl4 the transition state theory rate constants are in good agreement with the experiment, the rate constants for IAc and IAm-the two substrates reacting preferably via the PCET-are difficult to predict correctly. Consequently, the corresponding reaction barriers necessitate lowering by 1-3 kcal mol-1 to bring them in accord with experiment. The B2PLYP method provides a worthwhile improvement over the M06-2X energetics although the largest errors remain for the two PCET processes.