Rate constants for the gas‐phase reactions of hydroxyl radicals and chlorine atoms with aliphatic alcohols and ethers have been determined at 298 ± 2 K and at a total pressure of 1 atmosphere. The OH radical rate data were obtained using both the absolute technique of pulse radiolysis combined with kinetic UV spectroscopy and a conventional photolytic relative rate method. The Cl atom rate constants were measured using only the relative rate method. Values of the rate constants in units of 10⁻¹² cm³ molecule⁻¹ s⁻¹ are: (Formula Presented.) The above relative rate constants are based on the values of 𝓀(OH + c‐C₆H₁₂) = 7.49 × 10⁻¹² cm³ molecule⁻¹ s⁻¹ and 𝓀(Cl + c‐C₆H₁₂) = 311 × 10⁻¹² cm³ molecule⁻¹ s⁻¹. Attempts to corre late the trends in the rate constant data in terms of the bond dissociation energies and inductive effects are discussed.