In this work, the new catalyst (assigned as TBAPW₁₁Zn@TiO₂@PAni) was successfully designed and synthesized on the basis of quaternary ammonium salt of zinc monosubstituted phosphotungstate [(n‐C₄H₉)₄N][PW₁₁ZnO₃₉] (TBAPW₁₁Zn), titanium dioxide (TiO₂), and polyaniline (PAni). This study reports the catalytic oxidation‐extraction desulfurization (ECODS) of sulfur‐containing molecules from real and the simulated (Th, BT, and DBT) gasoline using new organic–inorganic hybrid catalyst (TBAPW₁₁Zn@TiO₂@PAni). The ECODS results were shown that the concentration of sulfur compounds (SCs) of real gasoline was lowered from 0.4992 to 0.0122 wt.% with 97% efficiency at 35 °C after 1 h. Furthermore, the synthesized heterogeneous nanocatalyst showed high stability and reusability after five times without significant loss of activity. The high performance of TBAPW₁₁Zn@TiO₂@PAni/H₂O₂/CH₃CO₂H system can be a promising route with a superb potential in the generation of ultra‐low‐sulfur gasoline. Also the Mann–Whitney U‐test results show that there is not a significant difference between the mean of sulfur percentage for DBT & BT, BT & Th and DBT & Th in the presence of the catalyst. Based on the Kruskal–Wallis test results, we can conclude that the temperature, time and amount of catalyst have a significant effect on ECODS efficiency of TBAPW₁₁Zn@TiO₂@PAni nanocomposite.