A strong hydrogen bond (H‐bond) exists in a binary mixture of dye aqueous solution (e.g. methylene blue, MB) with a ketone (e.g. acetone, AC) contamination. According to the limited literature and our preliminiary results, the MB in an MB/AC binary solution is not degradable (the decolorization percentage is <10%) within 30–40 min of the initiated oxidation process. In this study, we use a Bi‐doped TiO2 electro‐catalytic system, Fenton system, photo‐Fenton, and Bi‐doped or non‐doped TiO2 photocatalytic systems as the oxidation systems for MB/AC binary aqueous solutions. The results show that highly Bi‐doped TiO2 can be used as an effective catalyst in electro‐catalytic systems to realize an H‐bond stabilized dye solution with ketones; the decolorization percentage of electro‐catalytic systems is almost 60% within 30 min, which is better than that of 20% for the Fenton and photo‐Fenton catalytic oxidation systems.