Titanium and its alloys with various porous structures are one of the most important metals used in orthopaedic implants due to favourable properties as replacement for hard tissues. However, surface modification is critical to improve the osteointegration of titanium and its alloys. In this study, a bioactive magnesium coating was successfully fabricated on porous Ti6Al4V by means of arc ion plating, which was proved with fine grain size and high film/substrate adhesion. The surface composition and morphology were characterized by X-ray diffraction and SEM equipped with energy dispersive spectroscopy. Furthermore, the in vitro study of cytotoxicity and proliferation of MC3T3-E1 cells showed that magnesium coated porous Ti6Al4V had suitable degradation and biocompatibility. Moreover, the in vivo studies including fluorescent labelling, micro-computed tomography analysis scan and Van-Gieson staining of histological sections indicated that magnesium coated porous Ti6Al4V could significantly promote bone regeneration in rabbit femoral condylar defects after implantation for 4 and 8 weeks, and has better osteogenesis and osteointegration than the bare porous Ti6Al4V. Therefore, it is expected that this bioactive magnesium coating on porous Ti6Al4V scaffolds with improved osteointegration and osteogenesis functions can be used for orthopedic applications.