Nanofibrous mats were extensively studied as attractive membranes materials applied in the fields of biomedicine, filtration, catalysis, and biosensors due to their flexibility and porosity. In this current work, we have demonstrated an eco- friendly method for the preparation of novel three-dimensional silver nanoparticles (AgNPs)/titanium dioxide (TiO2)/hydrolyzed polyacrylonitrile (hPAN) nanostructures with favorable flowershaped architectures. It combined with electrospinning technique, liquid phase deposition method and photoreduction. The experimental results show that the TiO2 coating and AgNPs deposition increased the fiber surface roughness and specific surface area. And the results of antimicrobial activity assay revealed that the AgNPs/ TiO2/hPAN composites nanofibrous mats exhibited excellent antibacterial activity and the photocatalytic assay indicated that the mats prepared in 1 mM silver nitrate solution showed strong catalytic properties.