Recently, enols have been found to be the common intermediates in hydrocarbon combustion flames (Taatjes et al. Science 2005, 308, 1887), but the knowledge of kinetic properties for such species in combustion flames is rare. Therefore in this work, particular attention is paid to the formation of enols in combustion flames. Starting with HO and propene (CH(3)CH=CH(2)), the reaction mechanism involving eight product channels has been investigated systematically. It is revealed that the electrophilic addition of OH to the double bond of CH(3)CH=CH(2) is unselective and the chemically activated adducts, CH(3)CHOH=CH(2) and CH(3)CH=CH(2)OH, may undergo dissociation in competition with H-abstractions. The kinetics and product branching ratios of the HO and propene reaction have been evaluated in the temperature range of 200-3000 K by Variflex code, based on the weak collision master equation/microcanonical variational RRKM theory. Available experimental kinetic data can be quantitatively reproduced by this study, with a minor adjustment (1.0 kcal/mol) of the OH central addition barrier. From the theoretical calculations with multiple reflection correction included, the total rate constant is fitted to k(t) = 6.07 x 10(-5)T(-2.54) exp(108/T) cm(3) x molecule(-1) x s(-1) in the range of 200-800 K and k(t) = 7.11 x 10(-23)T(3.38) exp(-1097/T) cm(3) x molecule(-1) x s(-1) in the range of 800-3000 K, which are in close agreement with experimental data. The branching ratios of enol channels are consistent with the observation in low-pressure flames and hence the reaction mechanisms presented here provide valuable descriptions of enol formations in hydrocarbon combustion chemistry.