Electrospinning can be used to produce nanofiber mats. One of the often used polymers for electrospinning is polyacrylonitrile (PAN), especially for the production of carbon nanofibers, but also for a diverse number of other applications. For some of these applications—e.g., creation of nano-filters—the dimensional stability of the nanofiber mats is crucial. While relaxation processes—especially dry, wet and washing relaxation—are well-known and often investigated for knitted fabrics, the dimensional stability of nanofiber mats has not yet been investigated. Here we report on the wet relaxation of PAN nanofiber mats, which are dependent on spinning and solution parameters such as: voltage, electrode distance, nanofiber mat thickness, and solid content in the solution. Our results show that wet relaxation has a significant effect on the samples, resulting in a dimensional change that has to be taken into account for nanofiber mats in wet applications. While the first and second soaking in pure water resulted in an increase of the nanofiber mat area up to approximately 5%, the dried sample, after the second soaking, conversely showed an area reduced by a maximum of 5%. For soaking in soap water, small areal decreases between approximately 1–4% were measured.