In our study, mesoporous carbon fibers were prepared by using electrospinning and physical activation. In order to develop mesoporous structure, silica was used as a physical activation agent due to meso-size of particle. The diameter of activated carbon fibers increased and surface became rougher after physical activation. Textural properties of carbon fibers were evaluated by using surface pore structure analysis apparatus. The specific surface area increased 12 times and total pore volume increased about 57 times through physical activation using silica. The development of mesoporous structure was confirmed by pore size distribution and fraction of micropore volume. From the DFT pore size distribution, it is sure that broad meso-sized porous carbon fibers were obtained from physical activation in our experiment. The fact that fractions of micropore volume are too low showing less than 2% by the results of total pore volume and HK pore volume concedes that silica activated CFs are pretty mesoporous. Eventually activated carbon fibers having broad meso-sized pores were obtained successfully.