gamma-Radiolysis and measurements of halide ions by means of ion chromatography have been employed to investigate reductive dehalogenation of chloro-, bromo-, and iodophenols by carbon-centered radicals, (CH)-C-center dot(CH3)OH, (center dot)CHZOH, and (CO2-)-C-center dot, in oxygen-free aqueous solutions in the presence of ethanol, methanol, or sodium formate. While the reactions of 4-IC6H4OH with (CH)-C-center dot(CH3)OH and (CH2OH)-C-center dot radicals are endothermic in water/alcohol solutions, the addition of bicarbonate leads to iodide production in high yields, indicative of a chain reaction. The maximum effect has been observed with about 10 mM sodium bicarbonate present. The complex formed from an alpha-hydroxyalkyl radical and a bicarbonate anion is considered to cause the enhancement of the reduction power of the former to the extent at which the reduction of the iodophenol molecule becomes exothermic. No such effect has been observed with phosphate, which is a buffer with higher proton affinity, when added in the concentration of up to 20 mM at pH 7. This indicates that one-electron reduction reactions by a-hydroxyalkyl radicals occur by the concerted proton-coupled electron transfer, PCET, and not by a two-step ET/PT or PT/ET mechanisms. The reason for the negative results with phosphate buffer could be thus ascribed to a less stable complex or to the formation of a complex with a less suitable structure for an adequate support to reduce iodophenol. The reduction power of the carbonate radical anion is shown to be high enough to reduce iodophenols by a one-electron-transfer mechanism. In the presence of formate ions as H-atom donors, the dehalogenation also occurs by a chain reaction. In all systems, the chain lengths depend on the rate of reducing radical reproduction in the propagation step, that is, on the rate of H-atom abstraction from methanol, ethanol, or formate by 4-(C6H4OH)-C-center dot radicals liberated after iodophenol dehalogenation. The rate constants of those reactions were determined from the iodide yield measurements at a constant irradiation dose rate. They were estimated to be 6 M-1 s(-1) for methanol, 140 M-1 s(-1) for ethanol, and 2100 M-1 s(-1) for formate. Neither of the tested reducing C-centered radicals was able to dehalogenate the bromo or chloro derivative of phenol.