The relative rates of chlorine atom transfer from carbon tetrachloride to substituted benzyl radicals were determined from the ratio of products formed by chlorine transfer and combination of the radicals. Electron-donor substituents in the benzyl radical accelerate the reaction (ρ = -0.89). The experimental results were interpreted in terms of charge separation in the transition state. The transition states in hydrogen transfer from substituted toluenes to electrophilic radicals were found to be similar to those formed in chlorine transfer to substituted benzyl radicals.