A systematic investigation of the rate constants for hydrogen atom abstraction reactions by hydroxyl radicals on esters has been performed. The geometry optimizations and frequency calculations were obtained using the second-order Møller-Plesset method with the 6-311G(d,p) basis set. The same method was also used in order to determine the dihedral angle potential for each individual hindered rotor in each reactant and transition state. Intrinsic reaction coordinate calculations were used in order to connect each transition state to the corresponding local minimum. For the reactions of methyl ethanoate with an (•)OH radical, the relative electronic energies were calculated using the G3 and the CCSD(T)/cc-pVXZ (where X = D, T, and Q) methods, which were extrapolated to the complete basis set (CBS) limit. The electronic energies obtained using the G3 method were then benchmarked against the CBS results and were found to be within 1 kcal mol(-1) of one another. The high-pressure limit rate constants for every reaction channel were calculated by conventional transition-state theory, with an asymmetric Eckart tunneling correction, using the energies obtained with the G3 method. We report the individual, average, and total rate constants in the temperature range from 500 to 2200 K. Our calculated results are within a factor of 2 for methyl ethanoate and between 40% to 50% for methyl propanoate and methyl butanoate when compared to previously reported experimental data.