A simple method to prepare the Ag porous carbon nanofiber is reported. Ag porous carbon nanofiber was prepared by electrospinning and high temperature calcination. In this process, AgNO3-PMMA/PAN solution was the precursor solution of electrospinning, and Ag nanoparticles and pores were made by high temperature calcination. The catalytic activity of the Ag porous carbon nanofibers was confirmed by the styrene epoxidation. In the catalytic process, the conversation of styrene was 71% and the selectivity of styrene oxide was 83%.