Electrospinning, a process which allows the production of nanofibres, was recently rediscovered. Electrospinning uses the electrostatic attraction between an electrically charged polymer solution and a collector related to the ground. Polyamid-6 (PA-6) was electrospun in different spinning conditions such as the distance between needle tip and collector, the voltage and the needle tip geometry. Using scanning electron microscopy (SEM) and atomic force microscopy (AFM), the nanoweb longitudinal and cross-sectional morphologies were evidenced. Different morphologies, exhibiting various nanoroughnesses, were observed, which could be related to the experimental electrospinning parameters. These structural differences could be attributed to instability of the polymer jet and to the intrinsic behaviour of the electrospinning solution.