Background Here we report a new selenium-based heterogeneous catalyst, which was prepared from the immobilization of diphenyl diselenide on amine-functionalized Santa Barbara Amorphous-15 (SBA-15). The catalyst characterization study has been confirmed by different analysis methods including Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction patterns (XRD), field-emission scanning electron microscopy (FE-SEM), and Brunauer–Emmett–Teller (BET) surface area analysis. Results The newly designed catalyst was successfully applied in the green dehydration reaction of oximes to corresponding nitriles in the presence of hydrogen peroxide/air. To demonstrate the role of the catalyst in this study, the model reaction was also carried out in the absence of the catalyst and a trace yield of the relevant product was achieved. Conclusion In this way, a series of nitrile derivatives were obtained with 72–96% yields, also, the catalyst could be separated easily and recycled for four consecutive runs with no obvious drop in catalytic activity.