Although magnesium-based implants have good biocompatibility and biodegradability, they suffer from rapid corrosion in the body environment, which limits their biomedical applications. This study represents an approach for designing a bioactive and anti-corrosive hybrid structure composed of an inorganic layer by plasma electrolytic oxidation process and an organic layer of 3D printed polycaprolactone and amine-terminated polyethylene glycol scaffold containing dexamethasone. The results indicated that the hybrid layer exhibited superior adhesion strength, high corrosion resistance, remarkable biocompatibility, cell attachment, and osteogenic differentiation. The dexamethasone released from the 3D printed scaffold revealed high osteogenic differentiation capability. Hence, the fabrication of plasma electrolytic oxidized interlayer with a 3D printed scaffold can be a novel platform to preserve the magnesium-based biological implants from corrosion and to regenerate bone along with the controlled release of osteogenic components.