Polymer micro/nanofibres are prepared by typical and modified methods of electrospinning. The morphologies and microstructures of the electrospun micro/nanofibres are characterized by a scanning electron microscope (SEM). The micro/nanofibres prepared by the typical electrospinning are usually collected in the form of non-woven mats lacking of structural orientation. However, by modifying collector(s) of the electrospinning setup, the resulting polymer fibres show aligned structures to some extent. We analyse all the forces that the fibres experienced during electrospinning and find that the electrostatic force originating from the splitting electric field plays a key role in the alignment of the micro/nanofibres.