A sandwich-structured natural fiber-based magnetic composite, without the use of a binder, was developed in this study. It was fabricated via in situ synthesis, densification, and magnetron sputtering processes. The chemical composition, crystal structure, microstructure, and thermal stability were characterized via X-ray photoelectron spectroscopy, energy-dispersive spectroscopy, X-ray diffraction, scanning electron microscope, and thermogravimetric analysis. The hydrophobic, magnetic, and electromagnetic interference shielding properties were investigated by measuring the static water contact angle, the magnetic hysteresis loops, and the shielding effectiveness. The resulted composites exhibited a unique inner structure with a larger iron oxide size and content (492 nm and 26.1 wt%) on the interlayer surface in comparison to the core layer (135 nm and 18.7 wt%). The magnetic response can be controlled by the loaded iron oxide content and the copper film deposition. Sputtering copper film changed the surface free energy, and created rough micro-/nanostructures, which yielded a highly hydrophobic nature (133° in water contact angle), and approximately 99.2% of the electromagnetic energy was shielded by the 0.8 mm thick composite.