In this work, silver nanoparticles-containing polyacrylonitrile (PAN) solutions in N,N-dimethylformamide (DMF) were electrospun to be webs consisting of nanofibers. The inputted voltage and PAN content in the solution were fixed at 15 kV and 10 wt.% in DMF with 10 cm of tip-to-collector distance (TCD). The PAN/Ag nanofiber webs were stabilized by oxidation at 250 ${^{circ}C}$ for 2 h in air and carbonized at 1000 ${^{circ}C}$ for 2 h in $N_2$. The resultant diameter distribution and morphologies of the nanofibers were evaluated by scanning electron microscope analysis. The electrochemical behaviors of the nanofiber webs were also observed by cyclic voltammetry tests. It was found that the presence of silver nanoparticles in carbon nanofiber webs led to the increase of specific capacitance and the decrease of fiber diameters.