Bacterial infection is a major issue after artificial bone transplantation due to the absence of antibacterial function of bone scaffold, which seriously causes the transplant failure and even amputation in severe cases. In this study, oxygen vacancy (OV) defects Fe-doped TiO2 (OV-FeTiO2) nanoparticles were synthesized by nano TiO2 and Fe3O4 via high-energy ball milling, which was then incorporated into polycaprolactone/polyglycolic acid (PCLGA) biodegradable polymer matrix to construct composite bone scaffold with good antibacterial activities by selective laser sintering. The results indicated that OV defects were introduced into the core/shell-structured OV-FeTiO2 nanoparticles through multiple welding and breaking during the high-energy ball milling, which facilitated the adsorption of hydrogen peroxide (H2O2) in the bacterial infection microenvironment at the bone transplant site. The accumulated H2O2 could amplify the Fenton reaction efficiency to induce more hydroxyl radicals (·OH), thereby resulting in more bacterial deaths through ·OH-mediated oxidative damage. This antibacterial strategy had more effective broad-spectrum antibacterial properties against Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus). In addition, the PCLGA/OV-FeTiO2 scaffold possessed mechanical properties that match those of human cancellous bone and good biocompatibility including cell attachment, proliferation and osteogenic differentiation.