We have carried out ab initio calculations using Mo/ller–Plesset perturbation theory, scaling all correlation energy in second order (MP-SAC2) with several large basis sets, for the reaction OH+CH4→H2O+CH3. We found that correlation has a large effect on the geometry, barrier height, and vibrational frequencies of the transition state. The final calculated values, obtained with a correlation-balanced basis set, for the forward and reverse classical barrier heights are 7.9 and 21.2 kcal/mol, respectively. We have used these with transition state theory and an Eckart model for semiclassical tunneling calculations of the rate constants for the above reaction in the temperature range from 200 to 2000 K. We found that the present model, which requires information only at the reactants, transition state, and products, predicts rate constants of the same order of magnitude as the experimental data for this wide temperature range.