Fe3O4 nanoparticles were coated with silica followed by surface modification using a silylating agent and piperidine to obtain piperidinium benzene-1,3-disulfonate salt (PBDS) silica-coated magnetic nanoparticles (SCMNPs). The obtained catalyst was then analyzed using various characterization techniques, including thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) imaging, and X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), and energy-dispersive X-ray (EDX) analyses. The heterogeneous catalytic activity was investigated in one-pot pseudo-three-component synthesis of pyran derivatives, revealing efficient action and giving the products in high yield under green and sustainable conditions.