To obtain clean fuel, synthesis and characterization of a novel nanocomposite based on mono CdII‐substituted silicotungstate (K3SiW11CdO39), cobalt ferrite (CoFe2O4), and polyaniline (PAN) was presented for the first time. K3SiW11CdO39@CoFe2O4@PAN was identified by FT‐IR, XRD, SEM, and EDX techniques. The outcomes of the characterizations have shown that K3SiW11CdO39 and CoFe2O4 are uniformly dispersed on the PAN surface. The K3SiW11CdO39@CoFe2O4@PAN was employed as a heterogeneous catalyst in the extractive coupled oxidative desulfurization (ECOD) of both real gasoline and dibenzothiophene (DBT) as a thiophenic model fuel. Under relatively mild reaction conditions, the catalytic performance of the as‐prepared nanocatalyst in the ECOD procedure was studied by incorporating acetic acid/hydrogen proxied as an oxidant system at a volume ratio of 1:2. Based on the results, the K3SiW11CdO39@CoFe2O4@PAN nanocatalyst demonstrated effectiveness of up to 95% with 0.1 g at 35°C under optimal operating conditions in the ECOD process. Additionally, the synthesized nanocatalyst exhibited the ability to undergo five consecutive runs in the ECOD process without any discernible reduction in its activity.