Electrospinning can be used to create nanofiber mats from diverse polymers which can be used as filters etc. Depending on the spinning parameters, also nano-membranes, i.e. non-fibrous mats, can be produced as well as mixtures from both morphologies. The ratio of membrane to fibrous areas can be tailored by the distance between the high voltage electrode and substrate. Here the impact of the mat morphology on the water vapour permeability through polyacrylonitrile nanofiber mats with different membrane-like areas is shown, allowing for tailoring the permeability between 0.1 Pa · m²/W and more than 10 Pa · m²/W. In this way it is possible to create the finest filters as well as nearly impenetrable thin membranes with the same technology.