Polyvinylpyrrolidone electrospun membranes characterized by randomly, partially, or almost completely oriented nanofibers are prepared using a drum collector in static (i.e., 0 rpm) or rotating (i.e., 250 rpm or 500 rpm) configuration. Besides a progressive alignment alongside the tangential speed direction, the nanofibers show a dimension increasing with the collector rotating speed in the range 410-570 nm. A novel design of experiment approach based on a face-centred central composite design is employed to describe membrane mechanical properties using the computation of mathematical models and their visualization via response surface methodology. The results demonstrate the anisotropic nature of the fibre-oriented membranes with Young's modulus values of 165 MPa and 71 MPa parallelly and perpendicularly to the alignment direction, respectively. Above all, the proposed approach is proved to be a promising tool from an industrial point of view to prepare electrospun membranes with a tailored mechanical response by simply controlling the collector speed.