The nanomaterial is very popular in recent years. In this article, a new hybrid system by nickel oxide-modified Ag NPs/CNFs has been successfully produced by combining the electrospinning technique and calcination. Different proportions of nickel nitrate were mixed into the solution and the influence on the morphological structure of Ag nanoparticles was investigated, and then composite nanofibers were investigated, which indicated that Ag nanoparticles and NiO nanoparticles were uniform in size and dispersed homogeneously in the carbon nanofibers by different characterizations.