The electrochemical degradation of 4-chlorophenol and its main by-products was investigated in acid medium using binary oxides electrodes of nominal composition Ti/Ru0.3Ti0.7O2 and Ti/Ru0.3Sn0.7O2 prepared by thermal decomposition through two different routes: inorganic precursors dissolved in isopropanol and polymeric precursors (PPM). The aim of this study was to investigate the influence of both the composition and preparation methodology of these electrodes in the electrooxidation of the organic pollutants 4-chlorophenol and its by-products. Electrolyses were carried out using a filter press-type flow cell and monitored by high performance liquid chromatography (HPLC), total organic carbon (TOC), and chloride analyses. Besides CO2, the by-products formed in the reactions were 1,4-benzoquinone, 4-chlorocatechol, and hydroquinone, as well as oxalic, maleic, malic, malonic, and succinic acids. The electrocatalytic efficiency with respect to the degradation of by-products was evaluated through the electrooxidation of 1,4-benzoquinone and oxalic acid (OA). The anodes investigated in this work are very promising for the degradation of pollutants because of their excellent efficiency concerning the consumption of 4-chlorophenol and its by-products, although the mineralization of the starting material is not complete. The cleavage of the aromatic ring occurs preferentially in the case of electrodes prepared by decomposition of inorganic precursors due to their larger electrochemically active area and electrocatalytic activity for oxygen evolution reaction (OER). However, OA oxidation is favored on Ti/Ru0.3Sn0.7O2 prepared through decomposition of PPM.