The rate constants for the reactions of OH and OD with 2-methyl-3-buten-2-ol (MBO) have been measured at 2, 3, and 5 Torr total pressure over the temperature range 300-415 K using a discharge-flow system coupled with laser induced fluorescence detection of OH. The measured rate constants at room temperature and 5 Torr for the OH + MBO reaction in the presence of O-2 and the OD + MBO reaction are (6.32 +/- 0.27) and (6.61 +/- 0.66) x 10(-11) cm(3) molecule(-1) s(-1), respectively, in agreement with previous measurements at higher pressures. However, the rate constants begin to show a pressure dependence at temperatures above 335 K. An Arrhenius expression of k(0) = (2.5 +/- 7.4) x 10(-32) exp[(4150 +/- 1150)/T] cm(6) molecule(-2) s(-1) was obtained for the low-pressure-limiting rate constant for the OH + MBO reaction in the presence of oxygen. Theoretical calculations of the energetics of the OH + MBO reaction suggest that the stability of the different HO-MBO adducts are similar, with predicted stabilization energies between 27.0 and 33.4 kcal mol(-1) relative to the reactants, with OH addition to the internal carbon predicted to be 1-4 kcal mol(-1) more stable than addition to the terminal carbon. These stabilization energies result in estimated termolecular rate constants for the OH + MBO reaction using simplified calculations based on RRKM theory that are in reasonable agreement with the experimental values.