The development of Schwann cells, the principal glial cell in the peripheral nervous system, occurs through a series of transitional embryonic and postnatal phases, which is tightly regulated by a number of axonal signals. Electrospinning, widely used to fabricate nanofibrous scaffolds with required sizes and dimensions, makes it possible to replicate natural extracellular matrix. In the present study, Western-blot analysis revealed a down-regulation in expression of nerve growth factor and an up-regulation of laminin in RSC96 cells cultured on aligned electrospun fibers compared to cells seeded on other two polycaprolactone scaffolds. These results suggested that RSC96 cells may be directed towards the more maturation state induced by aligned electrospun fibers through contact guidance.