A novel design of a laboratory built axially rotating collector (ARC) having capability to align electrospun nanofibers have been described. A detailed morphological comparison of such nanofibers orientation and their geometry is done using scanning electron microscopy (SEM). For comparison various polymeric solutions were electrospun on conventional static collector as well as ARC. The average diameter of polyvinyl alcohol (PVA) nanofibers was found to be 250 nm while polycaprolactone (PCL) nanofibers were found to be within a range of 600–800 nm. Conducting nanoparticles such as graphene and multi-walled carbon nanotubes (MWNTs) mixed with polymer solutions shown to have a significant influence on the overall geometry of these nanofibers and their diameter distribution. It is evident from the SEM analysis that both graphene and MWNTs in polymer solution play a crucial role in achieving a uniform diameter of nanofibers. Lastly, the formation of the aligned nanofibers using ARC has been mathematically modeled and the electromagnetic field governing the process has been simulated.