This study focuses on the preparation and performance of an innovative, novel supported TiO2 photocatalyst to fix TiO2 Degussa P25 on Raschig glass rings. An interfacial electrostatically charged agent polyethylene-graft-maleic anhydride is used as a binder for the TiO2. This photocatalyst presented a stable performance during the degradation of phenolic waters. The photodegradation process was investigated as a function of (i) the concentration of the electron acceptor (H2O2), (ii) the intensity of the applied light, and (iii) the recirculation of the wastewaters in the photoreactor. The TiO2 catalyst was observed to maintain the pH at values close to 7 during the reactor treatment, enabling the treated phenolic waters to be discharged directly to a biological treating station. Modeling of the phenolic waters degradation was conducted through a single-exponential polynomial function. This gives a systematic way to determine the most economic use of the oxidant (H2O2) and electric energy required for the degradation process.