H and D atoms produced from the reaction of O(D-1) with isotopically substituted methanols have been measured by laser-induced fluorescence at 121.6 nm. At a collision energy of 7.3 kcal/mol, the product isotope ratios [H]/[D] are 0.26 +/- 0.03 and 7.1 +/- 0.8 for the reaction of O(D-1) with CH3OD and CD3OH, respectively. Measured isotopic branching ratios are discussed in terms of the site-selective attack of O(D-1) atoms to the C-H bond followed by preferential breaking of the new O-H bond. On the basis of the Doppler profiles of the H(D) atoms, the translational enegy released to the H(D) product channel is 9.5 +/- 0.5 kcal/mol. The reaction rate constant of D(D-1) with CH3OH is (5.1 +/- 0.1) x 10(-10) cm(3) molecule(-1) s(-1) at thermal collision energy (300 K) based on the measurement of the temporal decay of the O(D-1) atom signal with laser-induced fluorescence at 115.2 nm. The quantum yield for H atom formation is 0.18 +/- 0.02 over the total reaction processes.