Keggin-type H5PMo10V2O40 (PMoV2) immobilized onto amine-functionalized UiO-66-NH2 via acid-base interaction to create a highly efficient catalyst, called PMoV2@UiO-66-NH2, using post-synthetic modification. This POM-based MOF nanocomposite was used to synthesize carbonyl compounds from alcohols using H2O2 as an oxidant in a green oxidation process. The PMoV2 was successfully immobilized on the amine-functionalized MOF surface through electrostatic interaction, as confirmed by standard characterization methods including FT-IR, EDX, TGA, FE-SEM, MAP images, XRD, and ICP-OES. PMoV2@UiO-66-NH2 exhibited remarkable catalytic activity, with complete conversion of benzyl alcohol and high selectivity towards benzaldehyde. The superior catalytic performance of PMoV2@UiO-66-NH2 can be attributed to its large surface area, uniform dispersion of PMoV2, and the presence of V5+/V4+ redox pairs. The catalyst exhibited attractive yields, required minimal packing, and retained its catalytic activity for up to six cycles.