In this paper, a new type of inorganic-organic hybrid nanocatalyst has been prepared by the composition of the potassium salt of Cu-substituted phosphomolybdic acid (K5PMo11CuO39 abbreviated as PMoCu), magnesiocopperite (MgCu2O4) and polyvinyl alcohol (PVA). The assembled PMoCu-MgCu2O4@PVA composite was characterized by FT-IR, XRD, and SEM. The results of characterizations revealed that PMoCu and MgCu2O4 homogeneously dispersed on PVA surface. The PMoCu-MgCu2O4@PVA was exploited as a heterogeneous nanocatalyst for deep oxidative desulfurization (ODS) of gasoline and model oil. High desulfurization efficiency was achieved using hydrogen peroxide/acetic acid (H2O2/AcOH) as an oxidant at 35 degrees C after 60 min. On the basis of the suggested ODS system, the mercaptan and sulfur content of gasoline could be removed with 97% and 98% yield, respectively. The ODS of thiophene molecules, which are difficult to remove, could be reached to 97%. Also, PMoCu-MgCu2O4@PVA was demonstrated an excellent recyclability performance in the ODS reactions for five times without noticeable decrease in catalytic activity. It is believed that the present PMoCu-MgCu2O4@PVA/H2O2/AcOH system can be a convenient strategy to obtain clean gasoline fuel.