The properties of ceramic materials are dependent on crystal sizes and their distribution. These parameters can be controlled using electrospinning of the two-phase mixed system. The preceramic solution consists of silicon nanoparticles and polyacrylonitrile (PAN) polymer mixture. Particle distribution during the electrospinning technique was characterized using transmission electron microscopy and modeled using the finite element method. The experimental and numerical results were in agreement. Large silicon particles were located in the skin and the smaller ones were located at the core. This was illustrated by the migration rate from the core, which was the fastest for large particles and diminished as the particles become smaller in size. The threshold for Stokes number was found to be around 2.2 × 10-4 with a critical particle size of 1.0 × 10-7 m in diameter. The current results are very promising, as it demonstrated a novel way for the fabrication of PAN/Si ceramic nanofibers with a gradient of particle size and properties from the skin to the core.