3D printed scaffolds hold promising perspective for bone tissue regeneration. Inspired by process of bone de-velopment stage, 3D printed scaffolds with rapid internal vascularization ability and robust osteoinductionbioactivity will be an ideal bone substitute for clinical use. Here, we fabricated a 3D printed biodegradablescaffold that can control release deferoxamine, via surface aminolysis and layer-by-layer assembly technique,which is essential for angiogenesis and osteogenesis and match to bone development and reconstruction. Ourinvitrostudies show that the scaffold significantly accelerates the vascular pattern formation of human umbilicalendothelial cells, boosts the mineralized matrix production, and the expression of osteogenesis-related genesduring osteogenic differentiation of mesenchymal stem cells.In vivoresults show that deferoxamine promotesthe vascular ingrowth and enhances the bone regeneration at the defect site in a rat large bone defect model.Moreover, this 3D-printed scaffold has excellent biocompatibility that is suitable for mesenchymal stem cellsgrow and differentiate and possess the appropriate mechanical property that is similar to natural cancellousbone. In summary, this 3D-printed scaffold holds huge potential for clinical translation in the treatment ofsegmental bone defect, due to itsflexibility, economical friendly and practicality.