Segmental bone defects caused by trauma, tumor resection or congenital malformations are often reconstructed with autologous, allogeneic bone grafts or artificial bone materials, of which, about 5% ~ 10% will have delayed healing or even nonunion of fractures. The loss of periosteum and excessive accumulation of ROS in fracture site leads to the aging of osteoblasts and the decline of their proliferation and differentiation, thus affecting the fracture healing process. In this study, we prepared a functional modified artificial periosteum β‐TCP/MnO2/PCL(β‐TMP) by electrospinning with a function of catalyzing decomposition of H2O2. We examined the surface morphology of β‐TMP, the concentration of Ca, P and Mn of β‐TMP, as well as the diameter distribution range of nanofibers on β‐TMP. Through X‐ray diffraction patterns and Fourier transform infrared spectra, β‐TMP was characterized and its hydrophilicity was tested. The release of Mn2+ and Ca2+ of 0.1 and 0.05% β‐TMP in different pH values (7.4 and 5.5) determined by ICP. We also identified that β‐TMP could reduce the level of ROS in cells by lowering the level of H2O2. 0%, 0.05% and 0.1% β‐TMP displayed good cell compatibility, cell adhesion and cellular morphology in the condition with or without H2O2. 0.5% β‐TMP showed compromised cell compatibility in normal condition, however, the compromised phenotypes could be partially rescued in the present of H2O2. Compared with 0%, 0.05% and 0.1% β‐TMP displayed higher osteoblastic differentiation with or without H2O2 in BMSCs as well as in MG‐63. In sum, β‐TMP helped osteogenesis and promoted repair of bone defects.