In this study, a novel polyurethane (PU) nanofibrous mat doped with Ag-CoF NPs has been synthesized by electrospinning technique in which the in situ reduction of Ag+ into Ag NPs was achieved by utilizing the reduction ability of N,N-dimethylformamide (DMF), which played dual roles as a solvent and reducing agent. Typically, solgel consisting of CoF/PU and AgNO3 was stirred for 3 h and electrospun. The crystalline structure and uniform distribution of Ag-CoF NPs in/on PU NFs were demonstrated by X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. Two organic dyes, MB and RhB, were used to investigate the photocatalytic activity of the nanofibrous mat under visible light irradiation.