In this research, an unsymmetrical salen‐type oxo‐vanadium(IV) complex, [VO(salenac‐OH)] (salenac‐OH = [9‐(2′,4′‐dihydroxyphenyl)‐5,8‐diaza‐4‐methylnona‐2,4,8‐trienato](‐2)), was synthesized and covalently immobilized on the surface of magnetic γ‐Fe2O3 nanoparticles. The resulting γ‐Fe2O3@[VO(salenac‐OH)] nanoparticles were characterized by several techniques including Fourier transform infrared (FT‐IR) spectroscopy, X‐ray diffraction (XRD), scanning and transmission electron microscopies (SEM and TEM), energy‐dispersive X‐ray (EDX) spectroscopy, vibrating sample magnetometry (VSM), thermal gravimetric analysis (TGA), inductively coupled plasma (ICP), and elemental analysis. The prepared γ‐Fe2O3@[VO(salenac‐OH)] nanoparticle was utilized as an efficient catalyst for selective oxidation of sulfides to sulfoxides using 30% H2O2 as oxidant and oxidative coupling of thiols into disulfides with urea/H2O2 (UHP) as an oxidizing reagent. The products were achieved with good to excellent yields at room temperature with no over‐oxidation of sulfoxides and disulfides to unexpected by‐products. This catalyst can be magnetically recovered by applying an external magnet and reused for five continuous cycles in both oxidation reactions without a significant loss in its catalytic activity. Furthermore, the FT‐IR spectrum and XRD pattern of the recovered catalyst showed no critical change to those of the fresh one.