The pulsed laser photolysis (PLP)–laser-induced fluorescence (LIF) method has been used to study the kinetics at low temperatures of the reactions of the OH free radical with HCl (138–298 K), CH₄(178–298 K) and C₂H₆(138–298 K). In deriving rate constants for the reactions of OH with CH₄ and C₂H₆, small but significant corrections were made to allow for the fast secondary reactions between OH and the alkyl radicals produced in the primary reactions. The results are compared with predictions based on extrapolations of kinetic data obtained at higher temperatures, and limitations of the experimental method at low temperatures are considered. The rate constants for OH + CH₄ and OH + C₂H₆ are in reasonable agreement with values calculated using modified Arrhenius expressions which have been fitted to data obtained at higher temperatures, although our rate constant for OH + CH₄ at 216 K is significantly higher than a recent determination at 223 K by Vaghjiani and Ravishankara [Nature (London), 1991, 350, 406]. However, the rate constants for OH + HCl at lower temperatures deviate significantly from such predictions.