Stable and efficient SnO2 electrodes are very promising for effectively degrading refractory organic pollutants in wastewater treatment. In this regard, we firstly prepared Ti3+ self‐doped urchin‐like rutile TiO2 nanoclusters (TiO2‐xNCs) on a Ti mesh substrate by hydrothermal and electroreduction to serve as an interlayer for the deposition of Sb−SnO2. The TiO2‐xNCs/Sb−SnO2 anode exhibited a high oxygen evolution potential (2.63 V vs. SCE) and strong ⋅OH generation ability for the enhanced amount of absorbed oxygen species. Thus, the degradation results demonstrated its good rhodamine B (RhB), methylene blue (MB), alizarin yellow R (AYR), and methyl orange (MO) removal performance, with the rate constant increased 5.0, 1.9, 1.9, and 4.7 times, respectively, compared to the control Sb−SnO2 electrode. RhB and AYR degradation mechanisms are also proposed based on the results of high‐performance liquid chromatography coupled with mass spectrometry and quenching experiments. More importantly, this unique rutile interlayer prolonged the anode lifetime sixfold, given its good lattice match with SnO2 and the three‐dimensional concave–convex structure. Consequently, this work paves a new way for designing the crystal form and structure of the interlayers to obtain efficient and stable SnO2 electrodes for addressing dye wastewater problems.

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