Recently there has been an increasing interest in bioactive factors with robust osteogenic ability and angiogenesis function to repair bone defects. However, previously tested factors have not achieved satisfactory results due to low loading doses and a short protein half-life. Finding a validated stable substitute for these growth factors and apply it to the construction of porous scaffolds with the dual function of osteogenesis and angiogenesis is therefore vital for bone tissue regeneration engineering. Graphene oxide (GO) has attracted increasing attention due to its good biocompatibility, osteogenic, and angiogenic functions. This study aims to design a scaffold composed of mesoporous bioactive glasses (MBG) and GO to investigate whether the composite porous scaffold promotes local angiogenesis and bone healing. Our in vitro studies demonstrate that the MBG-GO scaffolds have better cytocompatibility and higher osteogenesis differentiation ability with rat bone marrow mesenchymal stem cells (rBMSCs) than the purely MBG scaffold. Moreover, MBG-GO scaffolds promote vascular ingrowth and, importantly, enhance bone repair at the defect site in a rat cranial defect model. The new bone was fully integrated not only with the periphery but also with the center of the scaffold. From these results, it is believed that the MBG-GO scaffolds possess excellent osteogenic-angiogenic properties which will make them appealing candidates for repairing bone defects. The novelty of this research is to provide a new material to treat bone defects in the clinic.