In this work, an efficient oxidative desulfurization (ODS) process of real gas oil and model oils was introduced using (TBA)4PW11Fe@TiO2@PVA phase-transfer catalyst. The catalyst was successfully prepared by the composition of the quaternary ammonium salt of mono iron-substituted phosphotungstate (abbreviated as (TBA)4PW11Fe), titanium dioxide (TiO2), and polyvinyl alcohol (PVA). The nanocomposite obtained was characterized through FT-IR, UV–vis, XRD, and SEM techniques. The spectroscopic characterization revealed that the (TBA)4PW11Fe was immobilized on the surface of TiO2@PVA. The results of catalytic tests showed the outstanding ODS performance of (TBA)4PW11Fe@TiO2@PVA in the removal of thiophenic compounds. Under optimized reaction conditions, the ODS efficiencies of benzothiophene (BT), dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT) reach 96, 99, 97, and 98%, respectively. The desulfurization system can be recycled five times with merely a slight decrease in activity.