The intrinsic reaction kinetics of the decomposition of dichloroacetic acid (DCA) using UV/H2O2 was studied. A complete mathematical model, including the effect of the absorbed radiation intensities and H2O2 concentration was developed. The results of the kinetic measurements were analysed using a complete mathematical model of the experimental device that was used for the laboratory operation (a differential reactor inside a recycle). In this way it was expected to obtain intrinsic kinetic parameters. Experimental data agree well with theoretical predictions esmploying just two kinetic parameters derived from the proposed reaction mechanism.