Nanofibers with ordered inorganic nanoparticles inside are great interesting for their potential applications in biomedical and photonics. In this work, yardlong-bean shaped nanofibers were fabricated by the combined technology of surface-initiated atom transfer radical polymerization (ATRP) and coaxial electrospinning process. Initially, the core shell nanospheres were prepared by surface-initiated ATRP of glycidyl methacrylate (GMA) from silica nanoparticles with ATRP initiators on surface. Subsequent coaxial electrospinning allows prepare cross-linked nanofibers with a linear-single-particle-array structure. Removal of the inorganic cores gave rise to nanofibers with uniformly dispersed-close-pore structure, which would be useful to drug delivery and catalyst carrying.