The combination of electrospinning with extrusion based 3D printing technology opens new pathways for micro- and nanofabrication, which can be applied in a wide range of applications. This simple and inexpensive method has been proven to fabricate 3D fibrous polystyrene structures with controlled morphology and micro- to nano-scale fibers diameter. The controllable movement of the nozzle allows precise positioning of the deposition area of the fibers during electrospinning. A programmed circular nozzle pattern results in the formation of controllable 3D polystyrene designed shapes with fiber diameters down to 550 nm. The assembly of the fibrous structures starts instantaneously, and a 4 cm tall and 6 cm wide sample can be produced within a 10 minutes electrospinning process. The product exhibits high stability at ambient conditions. The shape, size, and thickness of fibrous polystyrene structures can be easily controlled by tuning the process parameters. It is assumed that the build-up of 3D fibrous polystyrene structures strongly depends on charge induction and polarization of the electrospun fibers.
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