In this study, a magnetic asymmetric Salamo-based Zn complex (HL = salen type di-Schiff bases)-supported on the surface of modified FeO (FeO@HL-Zn) as a new catalyst was designed and characterized numerous analytical techniques such as FT-IR spectroscopy, XRD, EDS, ICP-AES, SEM, TEM, TGA and VSM. An efficient and sustainable synthetic protocol has been presented for the synthesis of silyl ether substructures the silyl protection of alcohols under mild conditions. The synthetic protocol involves a two-component solvent-free reaction between various hydroxyl-bearing substrates and hexamethyldisilazane (HMDS) as an inexpensive silylating agent using FeO@HL-Zn MNPs as a magnetically separable, recyclable and reusable heterogeneous catalyst. FeO@HL-Zn MNPs were also applied for the removal of silyl protecting groups from hydroxyl functions using water in CHCl under green conditions. The catalyst demonstrated good to excellent catalytic yield efficiency for both the reactions compared to the commercial metal-based catalysts under green conditions for a wide range of substrates.