Multifunctional materials have received considerable attention as they could integrate different functional components in one‐single platform. In this study, novel chitosan/Fe3O4/TiO2@TiO2 nanowire (NW) microspheres having extracellular matrix‐like fibrous surface and photothermal antibacterial property were synthesized through in situ hydrothermal growth of TiO2 NWs on chitosan/Fe3O4/TiO2 microspheres. It is found that the microspheres were spherical in morphology with a diameter of 100–300 µm and exhibited a hierarchical and nanofibrous feature. Their surface was mainly constructed by numerous TiO2 NWs with a diameter of 20– 30nm. In vitro biological evaluation indicates that the chitosan/Fe3O4/TiO2@TiO2 NW microspheres significantly enhanced attachment and proliferation of human umbilical vein endothelial cells compared with chitosan/Fe3O4/TiO2 nanocomposite microspheres due to the presence of nanofibrous surface. Moreover, the microspheres showed photothermal antibacterial property to inhibit the growth of bacteria due to the presence of Fe3O4 component.

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