Electrospun poly(ε-caprolactone) (PCL) fibers containing silver nanoparticles were successfully prepared from PCL solutions added silver collide. The silver collide were obtained by N, N-dimethylformamide (DMF) reducing silver nitrate (AgNO3). The effects of PCL concentration and the content of silver nanoparticles on composite fibers morphology were characterized by field-emission scanning electron microscopy (FESEM). The existence of Ag nanoparticles on the electrospun fibers was approved by X-Ray diffraction (XRD). Simultaneously, the contact angles of fiber membranes were measured. The results indicated that uniform fibers were obtained when PCL concentration was 9wt%, the average diameter of fiber was significantly decreased as increasing the amount of silver collide, and Ag nanoparticles were successfully incorporated into the PCL fibers.