Silver nanoparticles (Ag NPs)/cellulose acetate (CA) composite ultrafine fibers were successfully prepared by the electrospinning method. Water-soluble Ag NPs were directly mixed into CA polymer fibers to form organic–inorganic composite ultrafine fibers. The optical property of Ag NPs was measured by ultraviolet-visble spectrometer (UV-vis). The presence and identification of crystalline of Ag NPs were confirmed by XRD analysis. Transmission electron microscopy (TEM) images showed that silver nanoparticles (Ag NPs) with an average diameter of 5–15 nm were obtained and were well distributed in the CA ultrafine fibers. The morphologies of the as-prepared electrospun Ag NPs/CA composite ultrafine fibers were characterized by scanning electron microscopy (SEM) and TEM. The composition of fibers was characterized by FTIR spectrometer.