A di-azo dye, Congo Red (CR) was used as a model compound to investigate the degradation mechanism in hot compressed water (HCW). The unique properties of HCW facilitated the degradation efficiency without addition of any organic solvent. The influences of reaction time, temperature, initial dye concentration and amount of hydrogen peroxide (H2O2) on the degradation of CR and the removal of total organic carbon (TOC) from the product solution were investigated. The presence of H2O2 was found to enhance the degradation of CR. The results showed that the degradation yield could reach 99.0% with a solution of 100 ppm CR and 50 mM H2O2 at 150°C at the end of 60 min. Maximum conversion of the total organic carbon was recorded as 62.2%. Moreover, the effect of the presence of several co-existing negative ions such as SO4 2-, Cl-, CO32- were investigated. It was found that the presence of SO42- accelerated evidently the degradation of CR. The other chosen anions (CO32- and Cl-) had an inhibitory effect on the decolorization of CR. Finally, kinetic study was carried out and the order of the reaction was calculated as 0.37.