Chitosan (CS) / poly(vinyl alcohol) (PVA) blend nanofibers containing Ag-SiO2 nanoparticles (CS/PVA/Ag-SiO2 nanofibers) were successfully prepared by electrospinning using formic acid (HCOOH) as solvent in this paper. The morphology, diameter and structure of the electrospun nanofibers were examined by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS). And the diameter distribution of the nanofibers was measured by Image-Pro Plus. The results showed that the ideal nanofibers with the diameter in 85-165 nm can be obtained with the proper technical parameters as follows: the spinning voltage at 40 kV, the extruding speed at 0.5 mL/h and the collecting distance at 200 mm. The CS/PVA/Ag-SiO2 nanofibers will present potential applications in wound dressing and bandage etc.