Production of OH in the reaction of the neopentyl radical with O-2 has been measured by a laser photolysis/cw absorption method for various pressures and oxygen concentrations at 673, 700, and 725 K. The MIT Reaction Mechanism Generator (RMG) was used to automatically generate a model for this system, and the predicted OH concentration profiles are compared to present and literature experimental results. Several reactions significantly affect the OH profile. The experimental data provide useful constraints on the rate coefficient for the formally direct chemical activation reaction of neopentyl radical with O-2 to form OH (CH3)(3)CCH2 + O-2 -> OH + 3,3-dimethyloxetane (Rxn 1) At 673 K and 60 Torr, log k(1) (cm(3) molecule(-1) s(-1)) = -13.7 +/- 0.5. Absolute absorbance measurements on OH and I indicate that the branching ratio for R + O-2 to OH is about 0.03 under these conditions. The data suggest that the ab initio neopentyl + O-2 potential energy surface of Sun and Bozzelli is accurate to within 2 kcal mol(-1).