This work determines the rate constant of hydrogen peroxide decomposition in supercritical water. Experiments were conducted at pressures ranging from 5.0 to 34.0 MPa and for temperatures up to 450 degrees C. The rate of the homogeneous decomposition reaction is distinguished from the rate of the catalytic decomposition on the reactor surface by conducting experiments at different surface-to-volume ratios. The rate constant of H2O2 decomposition follows the expression k(s(-1)) = 10(13.4+/-1.2) exp[(-180 +/- 16 kJ/mol)/RT], providing a higher value than that derived from RRKM calculations. Comparison between experiments at supercritical conditions (P = 24.5 and 34.0 MPa) and experiments in high-pressure steam (P = 5.0 and 10.0 MPa) show that the efficiency of the catalytic surface reactions decreases significantly under supercritical conditions. The rate constant just mentioned was incorporated into a methanol oxidation model and the new prediction is compared with the experimental data of Rice et al. (1996), showing a distinct improvement compared to the original prediction.