Primary and secondary reactions involved in the thermal decomposition of NH2OH are studied with a combination of shock tube experiments and transition state theory based theoretical kinetics. This coupled theory and experiment study demonstrates the utility of NH2OH as a high temperature source of OH radicals. The reflected shock technique is employed in the determination of OH radical time profiles via multipass electronic absorption spectrometry. O-atoms are searched for with atomic resonance absorption spectrometry. The experiments provide a direct measurement of the rate coefficient, k(1), for the thermal decomposition of NH2OH. Secondary rate measurements are obtained for the NH2 + OH (5a) and NH2OH + OH (6a) abstraction reactions. The experimental data are obtained for temperatures in the range from 1355 to 1889 K and are well represented by the respective rate expressions: log[k/(cm(3) molecule(-1) s(-1))] (-10.12 +/- 0.20) + (-6793 +/- 317 K/T) (k(1)); log[k/(cm(3) molecule(-1) s(-1))] (-10.00 +/- 0.06) + (-879 +/- 101 K/T) (k(5a)); log[k/(cm(3) molecule(-1) s(-1))] = (-9.75 +/- 0.08) + (-1248 +/- 123 K/T) (k(6a)). Theoretical predictions are made for these rate coefficients as well for the reactions of NH2OH + NH2, NH2OH + NH, NH + OH, NH2 + NH2, NH2 + NH, and NH + NH, each of which could be of secondary importance in NH2OH thermal decomposition. The theoretical analyses employ a combination of ab initio transition state theory and master equation simulations. Comparisons between theory and experiment are made where possible. Modest adjustments of predicted barrier heights (i.e., by 2 kcal/mol or less) generally yield good agreement between theory and experiment. The rate coefficients obtained here should be of utility in modeling NOx in various combustion environments.