A simple and non-conventional electrospinning technique was employed for producing highly oriented Polyacrylonitrile (PAN) nanofibers. The PAN nanofibers were electrospun from 14 wt% solution of PAN in dimethylformamid (DMF) at 11 kv on a rotating drum with various linear speeds from 22.5 m/min to 67.7 m/min. The influence of take up velocity was investigated on the degree of alignment, internal structure and mechanical properties of collected PAN nanofibers. Using an image processing technique, the best degree of alignment was obtained for those nanofibers collected at a take up velocity of 59.5 m/min. Moreover, Raman spectroscopy was used for measuring molecular orientation of PAN nanofibers. Similarly, a maximum chain orientation parameter of 0.25 was determined for nanofibers collected at a take up velocity of 59.5 m/min.