AbstractStable 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 (TiO_2‐xNCs) on a Ti mesh substrate by hydrothermal and electroreduction to serve as an interlayer for the deposition of Sb−SnO₂. The TiO_2‐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.